Protein polyurethane alloys and layered materials including the same

ABSTRACT

Protein polyurethane alloys including one or more proteins dissolved within one or more polyurethanes. The protein polyurethane alloy may have one or more mechanical properties that are superior to the polyurethane in the absence of protein. The protein polyurethane alloys may be incorporated into a layered material including one or more protein polyurethane alloy layers.

REFERENCE TO SEQUENCE LISTING SUBMITTED ELECTRONICALLY

The content of the electronically submitted sequence listing in ASCIItext file (Name: 4431_0680002_Seqlisting_ST25.txt; Size: 5,132 bytes;and Date of Creation: Apr. 30, 2021) filed with the application isherein incorporated by reference in its entirety.

FIELD

This disclosure relates to protein polyurethane alloys comprising one ormore proteins dissolved in a polyurethane. In particular embodiments,this disclosure relates to protein polyurethane alloys including one ormore proteins dissolved only in the hard phase of a polyurethane. Insome embodiments, the protein polymer alloys can have the look, feel,and aesthetic and/or mechanical properties similar to natural leather,and can be used to make goods and articles previously prepared fromnatural leather.

BACKGROUND

Leather is a versatile product used across many industries, includingthe furniture industry, where leather is regularly used as upholstery,the clothing industry, where leather is used to manufacture pants andjackets, the shoe industry, where leather is used to prepare casual anddress shoes, the luggage industry, the handbag and accessory industry,and in the automotive industry. The global trade value for leather ishigh, and there is a continuing and increasing demand for leatherproducts. However, there are variety of costs, constraints, and socialconcerns associated with producing natural leather. Foremost, naturalleathers are produced from animal skins, and as such, requires raisingand slaughtering livestock. Raising livestock requires enormous amountsof feed, pastureland, water, and fossil fuels and contributes to air andwaterway pollution, through, for example, greenhouse gases like methane.Leather production also raises social concerns related to the treatmentof animals. In recent years, there has also been a fairly welldocumented decrease in the availability of traditional high qualityhides. For at least these reasons, alternative means to meet the demandfor leather are desirable.

BRIEF SUMMARY

The present disclosure provides protein polyurethane alloys suitable foruse in a variety of applications, including as a replacement for naturalleather.

A first embodiment (1) of the present disclosure is directed to aprotein polyurethane alloy comprising a protein dissolved within apolyurethane, where the protein is a protein other than a soy protein.

In a second embodiment (2), the protein polyurethane alloy of the firstembodiment (1) has a Dynamic Mechanical Analysis (DMA) tan(δ) peak at atemperature ranging from about −60° C. to about 30° C., and a second DMAmodulus transition onset temperature ranging from about 120° C. to about200° C.

In a third embodiment (3), the protein polyurethane alloy of the firstembodiment (1) or the second embodiment (2) is transparent.

In a fourth embodiment (4), the polyurethane of the protein polyurethanealloy of any one of embodiments (1)-(3) has a Young's modulus in theabsence of protein, and the protein polyurethane alloy has a Young'smodulus ranging from about 10% to about 600% greater than the Young'smodulus of the polyurethane in the absence of protein.

In a fifth embodiment (5), the polyurethane of the protein polyurethanealloy of any one of embodiments (1)-(3) has a Young's modulus in theabsence of protein, and the protein polyurethane alloy has a Young'smodulus ranging from about 40% to about 600% greater than the Young'smodulus of the polyurethane in the absence of protein.

In a sixth embodiment (6), the polyurethane of the protein polyurethanealloy of any one of embodiments (1)-(5) has a Young's modulus in theabsence of protein, and the protein polyurethane alloy has a Young'smodulus ranging from about 10 MPa to about 350 MPa greater than theYoung's modulus of the polyurethane in the absence of protein.

In a seventh embodiment (7), the polyurethane of the proteinpolyurethane alloy of any one of embodiments (1)-(5) has a Young'smodulus in the absence of protein, and the protein polyurethane alloyhas a Young's modulus ranging from about 25 MPa to about 350 MPa greaterthan the Young's modulus of the polyurethane in the absence of protein.

In an eighth embodiment (8), the polyurethane of the proteinpolyurethane alloy of any one of embodiments (1)-(5) has a Young'smodulus in the absence of protein, and the protein polyurethane alloyhas a Young's modulus ranging from about 100 MPa to about 350 MPagreater than the Young's modulus of the polyurethane in the absence ofprotein.

In a ninth embodiment (9), the protein polyurethane alloy of any one ofembodiments (1)-(8) has a Young's modulus ranging from about 50 MPa toabout 450 MPa.

In a tenth embodiment (10), the protein polyurethane alloy of any one ofembodiments (1)-(8) has a Young's modulus ranging from about 75 MPa toabout 450 MPa.

In an eleventh embodiment (11), the polyurethane of the proteinpolyurethane alloy of any one of embodiments (1)-(10) has a second DMAmodulus transition onset temperature in the absence of protein, and theprotein polyurethane alloy has a second DMA modulus transition onsettemperature in degrees Celsius ranging from about 5% to about 70%greater than the second DMA modulus transition onset temperature of thepolyurethane in the absence of protein.

In a twelfth embodiment (12), the polyurethane of the proteinpolyurethane alloy of any one of embodiments (1)-(10) has a second DMAmodulus transition onset temperature in the absence of protein, and theprotein polyurethane alloy has a second DMA modulus transition onsettemperature in degrees Celsius ranging from about 15% to about 70%greater than the second DMA modulus transition onset temperature of thepolyurethane in the absence of protein.

In a thirteenth embodiment (13), the polyurethane of the proteinpolyurethane alloy of any one of embodiments (1)-(12) has a second DMAmodulus transition onset temperature in the absence of protein, and theprotein polyurethane alloy has a second DMA modulus transition onsettemperature ranging from about 5° C. to about 100° C. greater than thesecond DMA modulus transition onset temperature of the polyurethane inthe absence of protein.

In a fourteenth embodiment (14), the polyurethane of the proteinpolyurethane alloy of any one of embodiments (1)-(12) has a second DMAmodulus transition onset temperature in the absence of protein, and theprotein polyurethane alloy has a second DMA modulus transition onsettemperature ranging from about 20° C. to about 80° C. greater than thesecond DMA modulus transition onset temperature of the polyurethane inthe absence of protein.

In a fifteenth embodiment (15), the polyurethane of the proteinpolyurethane alloy of any one of embodiments (1)-(12) has a second DMAmodulus transition onset temperature in the absence of protein, and theprotein polyurethane alloy has a second DMA modulus transition onsettemperature ranging from about 40° C. to about 80° C. greater than thesecond DMA modulus transition onset temperature of the polyurethane inthe absence of protein.

In a sixteenth embodiment (16), the protein polyurethane alloy of anyone of embodiments (1)-(15) has a second DMA modulus transition onsettemperature ranging from about 130° C. to about 200° C.

In a seventeenth embodiment (17), the protein polyurethane alloy of anyone of embodiments (1)-(15) has a second DMA modulus transition onsettemperature ranging from about 165° C. to about 200° C.

In an eighteenth embodiment (18), the protein of the proteinpolyurethane alloy of any one of embodiments (1)-(17) has an isoelectricpoint ranging from about 4 to about 5 and a lysine weight percentranging from about 1 wt % to about 100 wt %.

In a nineteenth embodiment (19), the polyurethane of the proteinpolyurethane alloy of any one of embodiments (1)-(18) has a tensilestrength in the absence of protein, and the protein polyurethane alloyhas a tensile strength ranging from about 5% to about 55% greater thanthe tensile strength of the polyurethane in the absence of protein.

In a twentieth embodiment (20), the polyurethane of the proteinpolyurethane alloy of any one of embodiments (1)-(18) has a tensilestrength in the absence of protein, and the protein polyurethane alloyhas a tensile strength ranging from about 15% to about 55% greater thanthe tensile strength of the polyurethane in the absence of protein.

In a twenty-first embodiment (21), the polyurethane of the proteinpolyurethane alloy of any one of embodiments (1)-(20) has a tensilestrength in the absence of protein, and the protein polyurethane alloyhas a tensile strength ranging from about 2 MPa to about 8 MPa greaterthan the tensile strength of the polyurethane in the absence of protein.

In a twenty-second embodiment (22), the polyurethane of the proteinpolyurethane alloy of any one of embodiments (1)-(20) has a tensilestrength in the absence of protein, and the protein polyurethane alloyhas a tensile strength ranging from about 5 MPa to about 8 MPa greaterthan the tensile strength of the polyurethane in the absence of protein.

In a twenty-third embodiment (23), the protein polyurethane alloy of anyone of embodiments (1)-(22) has a tensile strength ranging from about 7MPa to about 21 MPa.

In a twenty-fourth embodiment (24), the protein polyurethane alloy ofany one of embodiments (1)-(23) comprises about 10 wt % to about 50 wt %of the protein and about 50 wt % to about 90 wt % of the polyurethane.

In a twenty-fifth embodiment (25), the protein polyurethane alloy of anyone of embodiments (1)-(23) comprises about 20 wt % to about 35 wt % ofthe protein and about 65 wt % to about 80 wt % of the polyurethane.

In a twenty-sixth embodiment (26), the protein of the proteinpolyurethane alloy of any one of embodiments (1)-(25) is a protein otherthan collagen.

In a twenty-seventh embodiment (27), the polyurethane of the proteinpolyurethane alloy of any one of embodiemnts (1)-(26) has a moisturevapor transmission rate in the absence of protein, and the proteinpolyurethane alloy has a moisture vapor transmission rate ranging fromabout 20% to about 600% greater than the moisture vapor transmissionrate of the polyurethane in the absence of protein.

In a twenty-eighth embodiment (28), the polyurethane of the proteinpolyurethane alloy of any one of embodiments (1)-(27) has a moisturevapor transmission rate in the absence of protein, and the proteinpolyurethane alloy has a moisture vapor transmission rate ranging fromabout 30 g/m²/24 hr to about 500 g/m²/24 hr greater than the moisturevapor transmission rate of the polyurethane in the absence of protein.

In a twenty-ninth embodiment (29), the protein polyurethane alloy of anyone of embodiments (1)-(28) has a moisture vapor transmission rateranging from about 30 g/m2/24hr to about 1000 g/m²/24 hr.

A thirtieth embodiment (30) is directed to a soy protein polyurethanealloy comprising a soy protein dissolved within a polyurethane, wherethe soy protein polyurethane alloy has a Dynamic Mechanical Analysis(DMA) tan(δ) peak at a temperature ranging from about −60° C. to about30° C. and a second DMA modulus transition onset temperature rangingfrom about 130° C. to about 200° C.

In a thirty-first embodiment (31), the soy protein polyurethane alloy ofthe thirtieth embodiment (30) is transparent.

In a thirty-second embodiment (32), the polyurethane of the soy proteinpolyurethane alloy of the thirtieth embodiment (30) or the thirty-firstembodiment (31) has a Young's modulus in the absence of soy protein, andthe soy protein polyurethane alloy has a Young's modulus ranging fromabout 60% to about 570% greater than the Young's modulus of thepolyurethane in the absence of soy protein.

In a thirty-third embodiment (33), the polyurethane of the soy proteinpolyurethane alloy of any one of embodiments (30)-(32) has a Young'smodulus in the absence of soy protein, and the soy protein polyurethanealloy has a Young's modulus ranging from about 35 MPa to about 340 MPagreater than the Young's modulus of the polyurethane in the absence ofsoy protein.

In a thirty-fourth embodiment (34), the soy protein polyurethane alloyof any one of embodiments (30)-(33) has a Young's modulus ranging fromabout 90 MPa to about 400 MPa.

In a thirty-fifth embodiment (35), the polyurethane of the soy proteinpolyurethane alloy of any one of embodiments (30)-(34) has a second DMAmodulus transition onset temperature in the absence of soy protein, andthe second DMA modulus transition onset temperature of the soy proteinpolyurethane alloy ranges from about 15° C. to about 100° C. greaterthan the second DMA modulus transition onset temperature of thepolyurethane in the absence of soy protein.

In a thirty-sixth embodiment (36), the polyurethane of the soy proteinpolyurethane alloy of any one of embodiments (30)-(35) has a tensilestrength in the absence of soy protein, and the soy protein polyurethanealloy has a tensile strength ranging from about 10% to about 45% greaterthan the tensile strength of the polyurethane in the absence of soyprotein.

In a thirty-seventh embodiment (37), the polyurethane of the soy proteinpolyurethane alloy of any one of embodiments (30)-(36) has a tensilestrength in the absence of soy protein, and the soy protein polyurethanealloy has a tensile strength ranging from about 1.5 MPa to about 5.5 MPagreater than the tensile strength of the polyurethane in the absence ofsoy protein.

In thirty-eigth embodiment (38), the soy protein polyurethane alloy ofany one of embodiments (30)-(37) has a tensile strength ranging fromabout 14 MPa to about 19 MPa.

In a thirty-ninth embodiment (39), the soy protein polyurethane alloy ofany one of embodiments (30)-(38) comprises about 10 wt % to about 50 wt% of the soy protein and about 50 wt % to about 90 wt % of thepolyurethane.

In a fortieth embodiment (40), the soy protein polyurethane alloy of anyone of embodiments (30)-(38) comprises about 20 wt % to about 35 wt % ofthe soy protein and about 65 wt % to about 80 wt % of the polyurethane.

In a fourty-first embodiment (41), the polyurethane of the soy proteinpolyurethane alloy of any one of embodiments (30)-(40) has a moisturevapor transmission rate in the absence of protein, and the soy proteinpolyurethane alloy has a moisture vapor transmission rate ranging fromabout 20% to about 600% greater than the moisture vapor transmissionrate of the polyurethane in the absence of protein.

In a fourty-second embodiment (42), the polyurethane of the soy proteinpolyurethane alloy of any one of embodiments (30)-(41) has a moisturevapor transmission rate in the absence of protein, and the soy proteinpolyurethane alloy has a moisture vapor transmission rate ranging fromabout 30 g/m²/24 hr to about 500 g/m²/24 hr greater than the moisturevapor transmission rate of the polyurethane in the absence of protein.

In a fourty-third embodiment (43), the soy protein polyurethane alloy ofany one of embodiments (30)-(42) has a moisture vapor transmission rateranging from about 30 g/m²/24 hr to about 1000 g/m²/24 hr.

In a fourty-fourth embodiment (44), the protein of the soy proteinpolyurethane alloy of any one of embodiments (30)-(43) is soy proteinisolate.

In a fourty-fifth embodiment (45), the protein of the soy proteinpolyurethane alloy of any one of embodiments (40)-(43) is a chemicallymodified soy protein isolate.

BRIEF DESCRIPTION OF THE FIGURES

The accompanying figures, which are incorporated herein, form part ofthe specification and illustrate embodiments of the present disclosure.Together with the description, the figures further serve to explain theprinciples of and to enable a person skilled in the relevant art(s) tomake and use the disclosed embodiments. These figures are intended to beillustrative, not limiting. Although the disclosure is generallydescribed in the context of these embodiments, it should be understoodthat it is not intended to limit the scope of the disclosure to theseparticular embodiments. In the drawings, like reference numbers indicateidentical or functionally similar elements.

FIG. 1 is a dynamic mechanical analysis (DMA) graph of storage modulusversus temperature for various materials.

FIG. 2 is a graph showing the relationship between maximum tensilestress and gelatin weight percent for gelatin polyurethane alloysaccording to some embodiments.

FIG. 3 is a graph showing the relationship between Young's modulus andgelatin weight percent for gelatin polyurethane alloys according to someembodiments.

FIG. 4 is a DMA graph of storage modulus versus temperature for variousmaterials.

FIG. 5 is a graph showing the relationship between maximum tensilestress and soy protein isolate (SPI) weight percent for SPI polyurethanealloys according to some embodiments.

FIG. 6 is a graph showing the relationship between Young's modulus andSPI weight percent for SPI polyurethane alloys according to someembodiments.

FIG. 7 is a DMA graph of storage modulus versus temperature for variousmaterials.

FIG. 8A is a graph comparing the maximum tensile stress of variousprotein polyurethane alloys according to some embodiments.

FIG. 8B is a graph comparing the Young's modulus of various proteinpolyurethane alloys according to some embodiments.

FIG. 9 is a DMA thermogram comparing L3360 and a gelatin L3360 alloyaccording to some embodiments.

FIG. 10 is a DMA thermogram comparing Hauthane HD-2001 polyurethane anda gelatin Hauthane HD-2001 polyurethane alloy according to someembodiments.

FIG. 11 is a DMA thermogram comparing SANCURE™ 20025F polyurethane and agelatin SANCURE™ 20025F polyurethane alloy according to someembodiments.

FIG. 12 is a DMA thermogram comparing IMPRANIL® DLS polyurethane and agelatin IMPRANIL® DLS polyurethane alloy according to some embodiments.

FIG. 13 is a DMA thermogram comparing BONDTHANE™ UD-108 polyurethane anda gelatin BONDTHANE™ UD-108 polyurethane alloy according to someembodiments.

FIG. 14 is a DMA thermogram comparing BONDTHANE™ UD-303 polyurethane anda gelatin BONDTHANE™ UD-303 polyurethane alloy according to someembodiments.

FIG. 15 is a DMA thermogram comparing BONDTHANE™ UD-250 polyurethane anda gelatin BONDTHANE™ UD-250 polyurethane alloy according to someembodiments.

FIG. 16 is a representative DMA graph illustrating the methodology ofmeasuring first and second DMA modulus transition onset temperatures.

FIG. 17 illustrates a layered material according to some embodiments.

FIG. 18 illustrates a layered material according to some embodiments.

FIG. 19 is a block diagram illustrating a method for making a layeredmaterial according to some embodiments.

FIGS. 20A-20F illustrate a method of making a layered material accordingto some embodiments.

FIG. 21 illustrates a spacer fabric according to some embodiments.

FIG. 22 is a DMA thermogram comparing IMPRAPERM® DL 5249 polyurethaneand a soy protein isolate IMPRAPERM® DL 5249 alloy according to someembodiments.

FIG. 23 is a graph measuring the weight of water transported through theconstruction as weight change versus time for a multi-layer proteinpolyurethane alloy according to some embodiments.

DETAILED DESCRIPTION

The indefinite articles “a,” “an,” and “the” include plural referentsunless clearly contradicted or the context clearly dictates otherwise.

The term “comprising” is an open-ended transitional phrase. A list ofelements following the transitional phrase “comprising” is anon-exclusive list, such that elements in addition to those specificallyrecited in the list can also be present. The phrase “consistingessentially of” limits the composition of a component to the specifiedmaterials and those that do not materially affect the basic and novelcharacteristic(s) of the component. The phrase “consisting of” limitsthe composition of a component to the specified materials and excludesany material not specified.

Where a range of numerical values comprising upper and lower values isrecited herein, unless otherwise stated in specific circumstances, therange is intended to include the endpoints thereof, and all integers andfractions within the range. It is not intended that the disclosure orclaims be limited to the specific values recited when defining a range.Further, when an amount, concentration, or other value or parameter isgiven as a range, one or more ranges, or as list of upper values andlower values, this is to be understood as specifically disclosing allranges formed from any pair of any upper range limit or value and anylower range limit or value, regardless of whether such pairs areseparately disclosed. Finally, when the term “about” is used indescribing a value or an end-point of a range, the disclosure should beunderstood to include the specific value or end-point referred to.Whether or not a numerical value or end-point of a range recites“about,” the numerical value or end-point of a range is intended toinclude two embodiments: one modified by “about,” and one not modifiedby “about.”

As used herein, the term “about” refers to a value that is within ±10%of the value stated. For example, about 3 MPa can include any numberbetween 2.7 MPa and 3.3 MPa.

As used herein, a first layer described as “attached to” a second layermeans that the layers are attached to each other either by directcontact and attachment between the two layers or via one or moreintermediate adhesive layers. An intermediate adhesive layer can be anylayer that serves to attach a first layer to a second layer.

As used herein, the phrase “disposed on” means that a first component(e.g., layer) is in direct contact with a second component. A firstcomponent “disposed on” a second component can be deposited, formed,placed, or otherwise applied directly onto the second component. Inother words, if a first component is disposed on a second component,there are no components between the first component and the secondcomponent.

As used herein, the phrase “disposed over” means other components (e.g.,layers or substrates) may or may not be present between a firstcomponent and a second component.

As used herein, a “bio-based polyurethane” is a polyurethane where thebuilding blocks of polyols, such as diols and diacids like succinicacid, are derived from a biological material such as corn starch.

As used herein, the term “substantially free of” means that a componentis present in a detectable amount not exceeding about 0.1 wt %.

As used herein, the term “free of” means that a component is not presentin a blend or material (e.g., a protein polyurethane alloy), even intrace amounts.

As used herein “collagen” refers to the family of at least 28 distinctnaturally occurring collagen types including, but not limited tocollagen types I, II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII,XIV, XV, XVI, XVII, XVIII, XIX, and XX. The term collagen as used hereinalso refers to collagen prepared using recombinant techniques. The termcollagen includes collagen, collagen fragments, collagen-like proteins,triple helical collagen, alpha chains, monomers, gelatin, trimers andcombinations thereof. Recombinant expression of collagen andcollagen-like proteins is known in the art (see, e.g., Bell, EP1232182B1, Bovine collagen and method for producing recombinant gelatin;Olsen, et al., U.S. Pat. No. 6,428,978 and VanHeerde, et al., U.S. Pat.No. 8,188,230, incorporated by reference herein in their entireties)Unless otherwise specified, collagen of any type, whether naturallyoccurring or prepared using recombinant techniques, can be used in anyof the embodiments described herein. That said, in some embodiments, thecollagen described herein can be prepared using bovine Type I collagen.Collagens are characterized by a repeating triplet of amino acids,-(Gly-X-Y)n-, so that approximately one-third of the amino acid residuesin collagen are glycine. X is often proline and Y is oftenhydroxyproline. Thus, the structure of collagen may consist of threeintertwined peptide chains of differing lengths. Different animals mayproduce different amino acid compositions of the collagen, which mayresult in different properties (and differences in the resultingleather).

In some embodiments, the collagen can be chemically modified to promotesolubility in water.

Any type of collagen, truncated collagen, unmodified orpost-translationally modified, or amino acid sequence-modified collagencan be used as part of the protein polyurethane alloy.

In some embodiments, the collagen can be plant-based collagen. Forexample, the collagen can be a plant-based collagen made by CollPlant.

In some embodiments, a collagen solution can be fibrillated intocollagen fibrils. As used herein, collagen fibrils refer to nanofiberscomposed of tropocollagen or tropocollagen-like structures (which have atriple helical structure). In some embodiments, triple helical collagencan be fibrillated to form nanofibrils of collagen.

In some embodiments, a recombinant collagen can comprise a collagenfragment of the amino acid sequence of a native collagen moleculecapable of forming tropocollagen (trimeric collagen). A recombinantcollagen can also comprise a modified collagen or truncated collagenhaving an amino acid sequence at least 70, 80, 90, 95, 96, 97, 98, or99% identical or similar to a native collagen amino acid sequence (or toa fibril forming region thereof or to a segment substantially comprising[Gly-X-Y]n). In some embodiments, the collagen fragment can be a 50 kDaportion of a native collagen. Native collagen sequences include theamino acid sequences of CollA1, CollA2, and Col3A1, described byAccession Nos. NP_001029211.1, NP_776945.1 and NP_001070299.1, which areincorporated by reference. In some embodiments, the collagen fragmentcan be a portion of human collagen alpha-1(III) (Col3A1; Uniprot#P02461, Entrez Gene ID #1281). In some embodiments, the collagenfragment can comprise the amino acid sequence listed as SEQ ID NO: 1.

Methods of producing recombinant collagen and recombinant collagenfragments are known in the art. For example, U.S. Pub. Nos.2019/0002893, 2019/0040400, 2019/0093116, and 2019/0092838 providemethods for producing collagen and collagen fragments that can be usedto produce the recombinant collagen and recombinant collagen fragmentsdisclosed herein. The contents of these four publications areincorporated by reference in their entirety.

Protein polyurethane alloys described herein can comprise a protein thatis miscible with only one of a plurality of phases of a polyurethane, ora plurality of polyurethanes, with which it is blended. For example, insome embodiments, the protein polyurethane alloy can include a proteinthat is miscible with only the hard phase of the polyurethane, or theplurality of polyurethanes, having both a hard phase and a soft phase.Protein polyurethane alloys described herein can be free of orsubstantially free of protein in form of particles dispersed in apolyurethane. For example, in some embodiments, the protein polyurethanealloys can be free of or substantially free of protein particles havingan average diameter of greater than 1 micron (μm).

In some embodiments, the protein polyurethane alloys can be free of orsubstantially free of soy protein particles having an average diameterof greater than 1 micron (μm). In some embodiments, the proteinpolyurethane alloys can be free of or substantially free of collagenparticles having an average diameter of greater than 1 micron (μm). Insome embodiments, the protein polyurethane alloys can be free of orsubstantially free of gelatin particles having an average diameter ofgreater than 1 micron (μm). In some embodiments, the proteinpolyurethane alloys can be free of or substantially free of bovine serumalbumin particles having an average diameter of greater than 1 micron(μm). In some embodiments, the protein polyurethane alloys can be freeof or substantially free of pea protein particles having an averagediameter of greater than 1 micron (μm). In some embodiments, the proteinpolyurethane alloys can be free of or substantially free of egg whitealbumin particles having an average diameter of greater than 1 micron(μm). In some embodiments, the protein polyurethane alloys can be freeof or substantially free of casein protein particles having an averagediameter of greater than 1 micron (μm). In some embodiments, the proteinpolyurethane alloys can be free of or substantially free of peanutprotein particles having an average diameter of greater than 1 micron(μm). In some embodiments, the protein polyurethane alloys can be freeof or substantially free of edestin protein particles having an averagediameter of greater than 1 micron (μm). In some embodiments, the proteinpolyurethane alloys can be free of or substantially free of whey proteinparticles having an average diameter of greater than 1 micron (μm) Insome embodiments, the protein polyurethane alloys can be free of orsubstantially free of karanj a protein particles having an averagediameter of greater than 1 micron (μm). In some embodiments, the proteinpolyurethane alloys can be free of, or substantially free of, cellulaseparticles having an average diameter of greater than 1 micron (μm). Insome embodiments, the protein polyurethane alloys can be free of, orsubstantially free of, recombinant collagen fragment particles having anaverage diameter of greater than 1 micron (μm).

In particular embodiments, the present disclosure provides a uniquecombination of a protein and a polyurethane in which the protein isdissolved in only the hard phase of the polyurethane. The presentdisclosure also provides methods of making the protein polyurethanealloys described herein. The present disclosure also provides layeredmaterials including one or more of the protein polyurethane alloy layersand methods of making the layered materials. The protein polyurethanealloys and the protein polyurethane alloy layers can include one or moretypes of protein and one or more polyurethanes.

Proteins suitable for use in the alloys disclosed herein can beun-modified or chemically modified. In some embodiments, the protein canbe modified to facilitate miscibility of the protein with the hard phaseof the polyurethane. In some embodiments, the protein can be chemicallymodified to promote solubility in water. In such embodiments, thechemical modification to promote solubility in water can facilitatemiscibility of the protein with the hard phase of the polyurethane. Insome embodiments, the chemically modified protein can be a partiallyhydrolyzed protein. In some embodiments, the chemically modified proteincan be a protein modified by covalent attachment of hydrophilic polymerchains, such as polyethylene glycol (PEG) chains, to the protein.

Suitable polyurethanes for use in the protein polyurethane alloysdescribed herein include those that comprise at least two phasesincluding a “soft phase” and a “hard phase.” The soft phase is formedfrom polyol segments within the polyurethane that separate from theurethane-containing phase due to differences in polarity. Theurethane-containing phase is referred to as the hard phase. This phaseseparation is well known in the art and is the basis of the many of theproperties of polyurethanes.

The soft phase is typically elastomeric at room temperature, andtypically has a softening point or glass transition temperature (Tg)below room temperature. The Tg can be measured by Dynamic MechanicalAnalysis (DMA) and quantified by either the peak of tan(δ) or the onsetof the drop in storage modulus. Alternately, Tg can be measured byDifferential Scanning Calorimetry (DSC). In some cases, there can becrystallinity in the soft phase, which can be seen as a melting point,typically between 0° C. and about 60° C. For example, the peak in thetan(δ) curve at about 35° C. for UD-108 polyurethane in FIG. 13indicates crystallinity in the soft phase of the polyurethane.

The hard phase typically has a Tg or melting point above roomtemperature, more typically above about 80° C. The softening of the hardphase can be measured by measuring the onset of the drop in storagemodulus (sometimes referred to as stiffness) as measured by DMA.

The “soft phase” for the polyurethane or the protein polyurethane alloyincluding the polyurethane comprises the polyol component of thepolyurethane. Its function is to be soft and flexible at temperaturesabove its Tg to lend toughness, elongation, and flexibility to thepolyurethane. Typical soft segments can comprise polyether polyols,polyester polyols, polycarbonate polyols, and mixtures thereof. Theytypically range in molecular weight from about 250 daltons to greaterthan about 5 kiloDaltons. The “hard phase” for the polyurethane or theprotein polyurethane alloy including the polyurethane comprises theurethane segments of the polymer that are imparted by the isocyanate(s)used to connect the polyols along with short chain diols such as butanediol, propane diol, and the like. Typical isocyanates useful for thepresent polyurethanes include, but are not limited to, hexamethylenediisocyanate, isophorone diisocyanate, methylene diisocyanate, phenyldiisocyanate, and the like. These molecules are more polar and stifferthan the polyols used to make the soft segment. Therefore, the hardsegment is stiffer and has a higher softening point compared to the softsegment. The function of the hard phase is to provide, among otherproperties, strength, temperature resistance, and abrasion resistance tothe polyurethane.

In some embodiments described herein, the protein can be miscible withonly the hard phase, leaving soft phase transitions substantiallyunaltered. Without wishing to be bound particular theory, it is believedthat when the protein is dissolved in the hard phase, it significantlyincreases the temperature at which the hard phase begins to soften, thusincreasing the temperature resistance of the alloy described herein.Protein polyurethane alloys described herein can also have increasedstiffness and increased strength relative to the base polyurethane(i.e., the polyurethane by itself, in the absence of protein).

Protein polyurethane alloys and layers described herein can be formed byblending one or more proteins with one or more water-borne polyurethanedispersions in a liquid state and drying the blend. In some embodiments,the protein polyurethane alloys and layers described herein can beformed by blending one or more proteins dissolved or dispersed in anaqueous solution with one or more water-borne polyurethane dispersionsin a liquid state and drying the blend. In some embodiments, thepolyurethane dispersion can be ionic, and either anionic or cationic. Insome embodiments, the polyurethane dispersion can be nonionic. In someembodiments, the blended protein and polyurethane can be formed into asheet and can, in certain embodiments, be attached to a substrate layerusing a suitable attachment process, such as direct coating, alamination process or a thermo-molding process. In certain embodiments,the lamination process can include attaching the sheet to the substratelayer using an adhesive layer. In some embodiments, the blended proteinand polyurethane can be coated or otherwise deposited over a substratelayer to attach the blended protein and polyurethane to the substratelayer. In some embodiments, attaching the blended protein andpolyurethane to the substrate layer can result in a portion of theblended protein and polyurethane being integrated into a portion of thesubstrate layer.

In a protein polyurethane alloy including one or more miscible proteinsand polyurethanes, the one or more proteins can be dissolved within thehard phase of the one or more polyurethanes. The protein polyurethanealloy can include at least one protein miscible with the hard phase ofone or more polyurethanes in the alloy. In some embodiments, the proteinpolyurethane alloy can include a plurality of proteins and/or aplurality of polyurethane hard phases that are miscible with each other.In all of these embodiments, and without wishing to be bound by aparticular theory, the protein, or plurality of proteins, is believed tobe dissolved in the hard phase of the polyurethane, or plurality ofpolyurethanes.

One or more proteins dissolved within the hard phase of one or morepolyurethanes can form a homogenous mixture when blended. In someembodiments, the protein polyurethane alloy can include a plurality ofproteins dissolved within or more polyurethanes such that the proteinsand the polyurethane(s) form a homogenous mixture when blended anddried. Typically, the protein polyurethane alloy including a homogenousmixture of protein and polyurethane does not include a substantialamount of protein not dissolved in the polyurethane. That said, and insome embodiments, the protein polyurethane alloy can include a fractionof protein dispersed within the polyurethane.

In embodiments described herein, the miscibility of the protein with thehard phase of the polyurethane can increase the DMA modulus transitionsoftening onset temperature of the hard phase in a protein polyurethanealloy without significantly changing one or more other thermo-mechanicalproperties of the alloy relative to the thermo-mechanical properties ofthe polyurethane by itself. For example, the miscibility of the proteinwith the hard phase of the polyurethane can increase the DMA modulustransition onset temperature of the hard phase in the proteinpolyurethane alloy without significantly changing the DMA transitiontemperature of the soft phase in the alloy relative to the DMAtransition temperature of the soft phase of the polyurethane by itself.

The DMA transition temperature of the soft phase can be referred to asthe glass transition temperature (Tg) of a polyurethane or the proteinpolyurethane alloy. The DMA transition temperature of the soft phase, orTg, can be quantified as (i) the DMA storage modulus transition onsettemperature of the soft phase (referred to herein as the “first DMAmodulus transition onset temperature”) or (ii) the DMA tan(δ) peaktemperature corresponding to the soft phase. The DMA transitiontemperature of the hard phase can be measured by the onset of the dropin the storage modulus of the polyurethane or the polyurethane proteinalloy and can be quantified as the DMA modulus transition onsettemperature of the hard phase (referred to herein as the “second DMAmodulus transition onset temperature”). In some embodiments, the secondDMA modulus transition onset temperature of the protein polyurethanealloy can be above about 80° C. or above about 130° C.

Although many types of proteins are contemplated for use in the proteinpolyurethane alloys described herein including, for example, collagenand soy proteins, it is understood that for all of the embodimentsdisclosed herein, the protein can be a protein other than collagenand/or a protein other than a soy protein. Thus, in some embodiments,the protein dissolved in the protein polyurethane alloy can be a proteinother than collagen. In other embodiments, the protein dissolved in theprotein polyurethane alloy can be a protein other than a soy protein. Insome embodiments, the protein dissolved in the protein polyurethanealloy can be a protein other than collagen and a protein other than asoy protein. In some embodiments, the protein polyurethane alloy can befree of or substantially free of collagen. In some embodiments, theprotein polyurethane alloy can be free of or substantially free of soyprotein. In some embodiments, the protein polyurethane alloy can be freeof or substantially free of soy protein and collagen.

As previously discussed, the soft phase and the hard phase of thepolyurethane can be measured using Dynamic Mechanical Analysis (DMA).Accordingly, the one or more polyurethanes included in the proteinpolyurethane alloys described herein can have at least two DMAtransition temperatures, one corresponding to the soft phase and onecorresponding to the hard phase. The DMA transition temperature of thesoft phase can be quantified as a “first DMA modulus transition onsettemperature” or DMA tan(δ) peak temperature corresponding to the softphase. The DMA transition temperature of the hard phase can bequantified by a “second DMA modulus transition onset temperature.” Thefirst DMA modulus transition onset temperature or a DMA tan(δ) peaktemperature is a lower DMA transition temperature and the second DMAmodulus transition onset temperature is a higher DMA transitiontemperature.

Similarly, the protein polyurethane alloys described herein can have atleast two phases. The at least two phases can include the soft phase andthe hard phase. Different phases of the alloys can be measured andquantified in the same manner as described above for the polyurethanes.

The polyurethane or the protein polyurethane alloy having first andsecond DMA transition temperatures means that it has a first DMAtransition temperature that occurs at a lower temperature than thesecond DMA transition temperature. However, the first and secondtransition temperatures need not be sequential transition temperatures.Other DMA transition temperatures could occur between the first andsecond transitions.

In some embodiments, the first DMA modulus transition onset temperaturefor a polyurethane can be below 30° C. In some embodiments, the firstDMA modulus transition onset temperature for a polyurethane can rangefrom about −65° C. to about 30° C., including subranges. For example, insome embodiments, the first DMA modulus transition onset temperature fora polyurethane can be about −65° C., about −60° C., about −55° C., about−50° C., about −45° C., about −40° C., about −35° C., about −30° C.,about −25° C., about −20° C., about −15° C., about −10° C., about −5°C., about −1° C., 0° C., about 1° C., about 5° C., about 10° C., about15° C., about 20° C., about 25° C., or about 30° C., or within a rangehaving any two of these values as endpoints, inclusive of the endpoints.In some embodiments, the first DMA modulus transition onset temperatureof a polyurethane can be about −65° C. to about 30° C., about −65° C. toabout 25° C., about −65° C. to about 20° C., about −65° C. to about 15°C., about −65° C. to about 10° C., about −65° C. to about 5° C., about−65° C. to about 1° C., about −65° C. to 0° C., about −65° C. to about−1° C., about −65° C. to about −5° C., about −65° C. to about −10° C. ,about −65° C. to about −15° C. , about −65° C. to about −20° C., about−65° C. to about −25° C., about −65° C. to about −30° C., about −65° C.to about −35° C., about −65° C. to about −35° C., about −65° C. to about−40° C., or about −65° C. to about −45° C.

FIGS. 9-15 show DMA thermograms for various exemplary polyurethanes. Thefirst DMA modulus transition onset temperature (T_(onset1)) for eachexemplary polyurethane is the temperature at which the slope of thestorage modulus (E′) curve begins to decrease significantly for a firsttime. The methodology of measuring this value is exemplified in FIG. 16.DMA equipment, such a DMA-850 from TA Instruments, can be programed tocalculate this temperature automatically. Table 4 lists the first DMAmodulus transition onset temperatures automatically calculated from theDMA graphs in FIGS. 9-15 (see Example Nos. 1−7).

In some embodiments, the DMA tan(δ) peak temperature corresponding tothe soft phase of a polyurethane can be below 30° C. In someembodiments, the DMA tan(δ) peak temperature corresponding to the softphase of a polyurethane can range from about −60° C. to about 30° C.,including subranges. For example, in some embodiments, the DMA tan(δ)peak temperature corresponding to the soft phase of a polyurethane canbe about −60° C., about −55° C., about −50° C., about −45° C., about−40° C., about −35° C., about −30° C., about −25° C., about −20° C.,about −15° C., about −10° C., about −5° C., about −1° C., 0° C., about1° C., about 5° C., about 10° C., about 15° C., about 20° C., about 25°C., or about 30° C., or within a range having any two of these values asendpoints, inclusive of the endpoints. In some embodiments, the DMAtan(δ) peak temperature corresponding to the soft phase of apolyurethane can be about −60° C. to about 30° C., about −60° C. toabout 25° C., about −60° C. to about 20° C., about −60° C. to about 15°C., about −60° C. to about 10° C., about −60° C. to about 5° C., about−60° C. to about 1° C. about −60° C. to 0° C., about −60° C. to about−1° C., about −60° C. to about −5° C., about −60° C. to about −10° C. ,about −60° C. to about −15° C., about −60° C. to about −20° C., about−60° C. to about −25° C., about −60° C. to about −30° C., about −60° C.to about −35° C., or about −60° C. to about −40° C.

The DMA thermograms in FIGS. 9-15 show the DMA tan(δ) peak temperaturecorresponding to the soft phase for various exemplary polyurethanes.Like DMA modulus transition onset temperatures, DMA equipment, such aDMA-850 from TA Instruments, can be programed to calculate thistemperature automatically. Table 4 lists the DMA tan(δ) peak temperatureautomatically calculated from the DMA graphs in FIGS. 9-15 (see ExampleNos. 1−7).

In some embodiments, the second DMA modulus transition onset temperaturefor a polyurethane can be above 30° C. In some embodiments, the secondDMA modulus transition onset temperature for a polyurethane can rangefrom about 45° C. to about 165° C. For example, in some embodiments, thesecond DMA modulus transition onset temperature for a polyurethane canbe about 45° C., about 50° C., about 55° C., about 60° C., about 65° C.,about 70° C., about 75° C., about 80° C., about 85° C., about 90° C.,about 95° C., about 100° C., about 105° C., about 110° C., about 115°C., about 120° C., about 125° C., about 130° C., about 135° C., about140° C., about 145° C., about 150° C., about 155° C., about 160° C., orabout 165° C., or within any range having any two of these values asendpoints, inclusive of the endpoints. In some embodiments, the secondDMA modulus transition onset temperature for a polyurethane can be about45° C. to about 165° C., about 50° C. to about 160° C., about 55° C. toabout 155° C., about 60° C. to about 150° C., about 65° C. to about 145°C., about 70° C. to about 140° C., about 75° C. to about 135° C., about80° C. to about 130° C., about 85° C. to about 125° C., about 90° C. toabout 120° C., about 95° C. to about 115° C., or about 100° C. to about110° C.

The DMA thermograms in FIGS. 9-15 show the second DMA modulus transitiononset temperatures for various exemplary polyurethanes. The second DMAmodulus transition onset temperature (T_(onset2)) for each exemplarypolyurethane is the temperature at which the slope of the storagemodulus (E′) curve begins decrease significantly for a second time. Themethodology of measuring this value is exemplified in FIG. 16. DMAequipment, such a DMA-850 from TA Instruments, can be programed tocalculate this temperature automatically. Table 3 lists the second DMAmodulus transition onset temperatures automatically calculated from theDMA graphs in FIGS. 9-15 (see Example Nos. 1-7).

In some embodiments, the polyurethane can exhibit crystallinity in thesoft phase. This is common in polyether soft segments containingpolytetramethylene glycol and some polyester polyols. In suchembodiments, the polyurethane can exhibit at least three transitions:the Tg of the soft phase, the melting point of the soft phase, and themodulus transition of the hard phase. Such melting in the soft phasetypically occurs between 0° C. and about 60° C., when present. Inembodiments exhibiting crystallinity in the soft phase, the proteinpolyurethane alloy will typically still exhibit the melting in the softphase because the protein is miscible with the hard phase, leaving themechanical properties of the soft phase substantially unchanged.

In typical embodiments described herein, the protein polyurethane alloycan have a second DMA modulus transition onset temperature higher thanthe second DMA modulus transition temperature of the polyurethane inabsence of protein (i.e., the polyurethane by itself). It is believedthat this increase in the second DMA modulus transition onsettemperature in the alloy is due to the miscibility of the protein andthe hard phase of the polyurethane. This selective miscibility of theprotein is indicated by an increase in the second DMA modulus transitiononset temperature without a similar increase in DMA transitiontemperature of the soft phase (quantified by a first DMA modulustransition onset temperature or the DMA tan(δ) peak temperaturecorresponding to the soft phase). This selective miscibility can beutilized to control properties of the protein polyurethane alloy, forexample mechanical and thermal properties.

In some embodiments, the protein polyurethane alloys and/or the layeredmaterials described herein can have a look and feel, as well asmechanical properties, similar to natural leather. For example, theprotein polyurethane alloy layer or the layered material including theprotein polyurethane alloy layer can have, among other things, hapticproperties, aesthetic properties, mechanical/performance properties,manufacturability properties, and/or thermal properties similar tonatural leather. Mechanical/performance properties that can be similarto natural leather include, but are not limited to, tensile strength,tear strength, elongation at break, resistance to abrasion, internalcohesion, water resistance, breathability (quantified in someembodiments by a moisture vapor transmission rate measurement), and theability to be dyed with reactive dyes and to retain color when rubbed(color fastness). Haptic properties that can be similar to naturalleather include, but are not limited to, softness, rigidity, coefficientof friction, and compression modulus. Aesthetic properties that can besimilar to natural leather include, but are not limited to, dyeability,embossability, aging, color, color depth, and color patterns.Manufacturing properties that can be similar to natural leather include,but are not limited to, the ability to be stitched, cut, skived, andsplit. Thermal properties that can be similar to natural leatherinclude, but are not limited to, heat resistance and resistance tostiffening or softening over a significantly wide temperature range, forexample 25° C. to 100° C.

Desirable properties for the protein polyurethane alloy describedherein, include but are not limited to, optical properties, hapticproperties, aesthetic properties, thermal properties, mechanicalproperties, and/or breathability properties. Exemplary thermalproperties include heat resistance and resistance to melting, and can bequantified by, for example, measuring the second modulus transitiononset temperature (T_(onset2)) of a material. Exemplary mechanicalproperties include abrasion resistance, maximum tensile stress (alsoreferred to as “tensile strength”), and Young's modulus. Unlessotherwise specified, maximum tensile stress values and Young's modulusvalues disclosed herein are measured according the methods provided byASTM D638. Exemplary breathability properties include moisture vaportransmission rate (MVTR) measured in g/m²/24 hr (grams per meterssquared per 24 hours). Unless otherwise specified, moisture vaportransmission rates disclosed herein are measured according to themethods provided by ASTM E96-Method B.

In some embodiments, the protein polyurethane alloy can be transparent.In some embodiments, a transparent protein polyurethane alloy canindicate that the protein is miscible with the hard phase of thepolyurethane in the alloy. As used herein, a “transparent” materialmeans material having an opacity of about 50% or less. Opacity ismeasured by placing a sample of material over a white background tomeasure the Y tristimulus value (“Over white Y”) in reflectance with aspectrometer using the D65 10 degree illuminant. The same sample is thenplaced over a black background and the measurement is repeated, yielding“Over black Y”. Percent opacity is calculated as “Over black Y” dividedby “Over white Y” times 100. 100% opacity is defined as lowesttransparency and 0% opacity is defined as the highest transparency.

In some embodiments, the protein polyurethane alloy can be transparentand can have an opacity ranging from 0% to about 50%, includingsubranges. For example, the transparent protein polyurethane alloy, canhave an opacity ranging from 0% to about 40%, 0% to about 30%, 0% toabout 20%, 0% to about 10%, or 0% to about 5%. The transparency of theprotein polyurethane alloy is evaluated before dying or otherwisecoloring the protein polyurethane alloy.

A transparent protein polyurethane alloy can be created by selecting andblending the appropriate combination of one or more proteins and one ormore polyurethanes. While not all combinations of protein andpolyurethane will result in a transparent protein polyurethane alloy, itis within the skill of the ordinarily skilled artisan to identifywhether a given blend results in a transparent protein polyurethanealloy in view of this disclosure. In embodiments directed to a layeredmaterial including a transparent protein polyurethane alloy layerdescribed herein, the transparent protein polyurethane alloy layer canprovide unique characteristics for the layered material. For example,compared to a non-transparent layer, the transparent proteinpolyurethane alloy layer can provide unique depth of color when dyed.Likewise, the transparent protein polyurethane alloy layer can provideits mechanical properties to the layered material without significantlyinfluencing the aesthetic properties of the material.

In some embodiments, the protein polyurethane alloy can include one ormore coloring agents. In some embodiments, the coloring agent can be adye, for example a fiber reactive dye, a direct dye, or a natural dye.Exemplary dyes, include but are not limited to, Azo structure acid dyes,metal complex structure acid dyes, anthraquinone structure acid dyes,and azo/diazo direct dyes. In some embodiments, the coloring agent canbe pigment, for example a lake pigment.

Suitable polyurethanes for blending with one or more proteins accordingto embodiments described herein include, but are not limited to,aliphatic polyurethanes, aromatic polyurethanes, bio-basedpolyurethanes, or acrylic acid modified polyurethanes. Suitablepolyurethanes are commercially available from manufacturers includingLubrizol, Hauthaway, Stahl, and the like. In some embodiments, apolyurethane for a protein polyurethane alloy can be bio-polyurethane.In some embodiments, the polyurethane is a water-dispersiblepolyurethane. In some embodiments, the polyurethane can be a polyesterpolyurethane. In some embodiments, the polyurethane can be a polyetherpolyurethane. In some embodiments, the polyurethane can be apolycarbonate-based polyurethane. In some embodiments, the polyurethanecan be an aliphatic polyester polyurethane. In some embodiments, thepolyurethane can be an aliphatic polyether polyurethane. In someembodiments, the polyurethane can be an aliphatic polycarbonatepolyurethane. In some embodiments, the polyurethane can be an aromaticpolyester polyurethane. In some embodiments, the polyurethane can be anaromatic polyether polyurethane. In some embodiments, the polyurethanecan be an aromatic polycarbonate polyurethane.

In some embodiments, the polyurethane can have a soft segment selectedfrom the group consisting of: polyether polyols, polyester polyols,polycarbonate polyols, and mixtures thereof. In some embodiments, thepolyurethane can have a hard segment comprising diisocyanates andoptionally short chain diols. Suitable diisocyanates can be selectedfrom the group consisting of: aliphatic diicocyanates such ashexamethylene diisocyanate, isophorone diisocyanate; aromaticdiisocyanates such as 4,4′ diphenyl methylene diisocyanate, toluenediisocyanate, phenyl diisocyanate, and mixtures thereof. Suitable shortchain diols include ethylene glycol, propane diol, butane diol, 2,2methyl 1,3 propane diol, pentane diol, hexane diol and mixtures thereof.In some embodiments crosslinkers such as multifunctional alcohols, forexample, trimethylol propane triol, or diamines such as ethylene diamineor 4,4′ diamino, diphenyl diamine.

Exemplary commercial polyurethanes, include but are not limited to L3360and Hauthane HD-2001 available from C.L. Hauthaway & Sons Corporation,SANCURE™ polyurethanes available from Lubrizol Corporation, BONDTHANE™polyurethanes, for example UD-108, UD-250, and UD-303 available fromBond Polymers International, and EPOTAL® ECO 3702 and EPOTAL® P100 ECOfrom BASF. L3360 is a aliphatic polyester polyurethane polymer aqueousdispersion having a 35% solids content, a viscosity of 50 to 500 cps(centipoise), and a density of about 8.5 lb/gal (pounds per gallon).HD-2001 is an aliphatic polyester polyurethane polymer aqueousdispersion having a 40% solids content, a viscosity of 50 to 500 cps,and a density of about 8.9 lb/gal. BONDTHANE™ UD-108 is an aliphaticpolyether polyurethane polymer aqueous dispersion having a 33% solidscontent, a viscosity of 300 cps, and a density of 8.7 lb/gal. BONDTHANE™UD-250 is an aliphatic polyester polyurethane polymer aqueous dispersionhaving a 35% solids content, a viscosity of 200 cps, and a density of8.8 lb/gal. BONDTHANE™ UD-303 is an aliphatic polyether polyurethanepolymer aqueous dispersion having a 35% solids content, a viscosity ofless than 500 cps, and a density of 8.7 lb/gal. EPTOAL® P100 ECO is apolyester polyurethane elastomer aqueous dispersion having approximately40% solids and a viscosity of about 40 mPas.

Exemplary bio-based polyurethanes include, but are not limited to, L3360available from C.L. Hauthaway & Sons Corporation, IMPRANIL® Eco DLS,IMPRANIL® Eco DL 519, IMPRANIL® Eco DLP-R, and IMPRAPERM® DL 5249available from Covestro. IMPRANIL® Eco DLS is an anionic, aliphaticpolyester polyurethane polymer aqueous dispersion having approximately50% solids content, a viscosity of less than 1,200 MPa·s, and a densityof about 1.1 g/cc. IMPRANIL® Eco DL 519 is an anionic, aliphaticpolyester polyurethane polymer aqueous dispersion. IMPRANIL® Eco DLP-Ris an anionic, aliphatic polyester polyurethane polymer aqueousdispersion. IMPRAPERM® DL 5249 is an anionic aliphaticpolyester-polyurethane polymer aqueous dispersion.

In some embodiments, the polyurethane can include reactive groups thatcan be cross-linked with a protein. Exemplary reactive groups include,but are not limited to, a sulfonate, an aldehyde, a carboxylic acid orester, a blocked isocyanate, or the like, and combinations thereof. Insuch embodiments, the polyurethane can be crosslinked to the protein inthe protein polyurethane alloy through the reaction of a reactive groupon the protein with the reactive group present in the polyurethane.

Suitable proteins for blending with one or more polyurethanes accordingto embodiments described herein include, but are not limited to,collagen, gelatin, bovine serum albumin (BSA), soy proteins, peaprotein, egg white albumin, casein, peanut protein, edestin protein,whey protein, karanj a protein, and cellulase. Suitable collagensinclude, but are not limited to, recombinant collagen (r-Collagen), arecombinant collagen fragment, and extracted collagens. Suitable soyproteins include, but are not limited to, soy protein isolate (SPI),soymeal protein, and soy protein derivatives. In some embodiments, thesoy protein isolate can be partially hydrolyzed soy protein isolate.Suitable pea proteins include, but are not limited to, pea proteinisolate, and pea protein derivatives. In some embodiments, the peaprotein isolate can be partially hydrolyzed pea protein isolate.

Table 1 below lists some exemplary proteins and properties of theproteins. The gelatin is gelatin from porcine skin, Type A (SigmaAldrich G2500). The collagen is extracted bovine collagen purchased fromWuxi BIOT Biology-technology Company. The bovine serum albumin SigmaAldrich 5470 bovine serum albumin. The r-Collagen is recombinantcollagen from Modern Meadow. The soy protein isolate is soy proteinisolate purchased from MP Medicals (IC90545625). The pea protein is peaprotein powder purchased from Bobs Red Mills (MTX5232). The egg whitealbumin protein is albumin from chicken egg white (Sigma Aldrich A5253).The casein protein is casein from bovine milk (Sigma Aldrich C7078). Thepeanut protein is peanut protein powder purchased from Tru-Nut. The wheyprotein is whey from bovine milk (Sigma Aldrich W1500). Other suitablesoy protein isolates include, but are not limited to, soy proteinisolate purchased from AMD (Clarisoy 100, 110, 150, 170, 180), or DuPont(SUPRO® XT 55, SUPRO® XT 221D, and SOBIND® Balance). Other suitable peaprotein powders include, but are not limited to, pea protein powderpurchased from Puns (870 and 870H).

Karanj a protein is a protein found in Karanj a seeds harvested fromPongamia pinnata trees (also known as Pongamia glabra trees). SeeRahman, M M., and Netravali, “Green Resin from Forestry Waste Residue‘Karanj a (Pongamia pinnata) Seed Cake’ for Biobased CompositeStructures,” ACS Sustainable Chem. Eng., 2: 2318−2328 (2014); see alsoMandal et al., “Nutritional Evaluation of Proteins from threeNon-traditional Seeds with or without Amino Acids Supplementation inAlbino Rats,” Proc. Indian natn. Sci. Acad., B50, No. 1, 48-56 (1984).The protein can be extracted from Karanja seeds using a solventextraction process. Id. In some embodiments, the karanja protein can bekaranja protein isolate. In such embodiments, karanja protein isolatecan be obtained by alkaline extraction and acid precipitation ofdefatted karanja seed cake. See Rahman, M M., and Netravali, “GreenResin from Forestry Waste Residue ‘Karanja (Pongamia pinnata) Seed Cake’for Biobased Composite Structures,” ACS Sustainable Chem. Eng., 2:2318-2328 (2014).

Suitable cellulase proteins are listed below in Table 1. The“Cellulase-RG” protein is Native Trichoderma sp. Cellulase availablefrom CREATIVE ENZYMES®. The “Cellulase-IG” protein is laboratory gradecellulase available from Carolina Biological Supply Company.

The 50 KDa recombinant collagen fragment (50 KDa r-Collagen fragment) inTable 1 is a collagen fragment comprising the amino acid sequence listedas SEQ ID NO: 1.

The “dissolution method” listed in Table 1 is an exemplary aqueoussolvent in which the protein can be dissolved in a solution that ismiscible with the hard phase of the polyurethane as described herein.Proteins that can be at least partly dissolved in an aqueous solutionare suitable for forming protein polyurethane alloys with polyurethanedispersions.

TABLE 1 Example Proteins Amino Acid Comp.: Protein Protein ProteinDissolution Molecular Isoelectric Lysine Thermostability Name SourceMethod Weight Point (g/100 g) up to 200° C. Gelatin Porcine Water ~100KDa ~4.8 2.6 Yes Collagen Bovine Water ~120 KDa — 2.2 — BSA Bovine Water~66 KDa ~4.7 11.98 — (Bovine Serum Albumin) r-Collagen Yeast Water ~100KDa — 3.6 — Soy protein Soy Water + ~30 to 60 KDa ~4.0 to 5.0 5.6 Yesisolate NaOH Pea Protein Pea Water + ~ 60 to 80 KDa ~4.5 7.6 Yes NaOHEgg White Chicken Egg Water ~40 KDa ~4.8 5.7 Yes Albumin Casein BovineMilk Water + ~24 KDa ~4.6 7.4 — NaOH Peanut Peanut Water + ~60 KDa ~4.52.5 Yes Protein NaOH Whey Bovine Milk Water ~18 KDa ~4.5 to 5.2 9.7 NoKaranja Karanja Seed Water — — 14.6 — protein isolate 50 KDa r- YeastWater ~50 KDa ~9.3 3.9 — Collagen fragment Cellulase- Trichoderma Water~20 to 90 KDa ~4.6 to 6.9 — — RG reesei Cellulase-IG Trichoderma Water —— — — reesei

In some embodiments, the protein can have one or more of the followingproperties: (i) a molecular weight within a range described herein (ii)an isoelectric point within a range described below, (iii) an amino acidcomposition measured in grams of lysine per 100 grams of protein in arange described below, and (iv) protein thermo-stability up to 200° C.

Protein Molecular Weight

In some embodiments, the protein can have a molecular weight rangingfrom about 1 KDa (kilodaltons) to about 700 KDa, including subranges.For example, the protein can have a molecular weight ranging from about1 KDa to about 700 KDa, about 10 KDa to about 700 KDa, about 20 KDa toabout 700 KDa, about 50 KDa to about 700 KDa, about 100 KDa to about 700KDa, about 200 KDa to about 700 KDa, about 300 KDa to about 700 KDa,about 400 KDa to about 700 KDa, about 500 KDa to about 700 KDa, about600 KDa to about 700 KDa, about 1 KDa to about 600 KDa, about 1 KDa toabout 500 KDa, about 1 KDa to about 400 KDa, about 1 KDa to about 300KDa, about 1 KDA to about 200 KDa, about 1 KDa to about 100 KDa, about 1KDa to about 50 KDa, about 1 KDa to about 20 KDa, or about 1 KDa toabout 10 KDa, or within a range having any two of these values asendpoints, inclusive of the endpoints.

Protein Isoelectric Point

In some embodiments, the protein can have an isoelectric point rangingfrom about 4 to about 10, including subranges. For example, the proteincan have an isoelectric point ranging from about 4 to about 10, about4.5 to about 9.5, about 5 to about 9, about 5.5 to about 8.5, about 6 toabout 8, about 6.5 to about 7.5, or about 6.5 to about 7, or within arange having any two of these values as endpoints, inclusive of theendpoints. In some embodiments, the protein can have an isoelectricpoint ranging from about 4 to about 5.

Protein Amino Acid Composition

In some embodiments, the protein can have an amino acid compositionmeasured in grams of lysine per 100 grams of protein (as referred to asa “lysine weight percent”) ranging from about 0.5 wt % to about 100 wt%, including subranges. For example, the protein can have a lysineweight percent ranging from about 0.5 wt % to about 100 wt %, about 1 wt% to about 100 wt %, about 5 wt % to about 100 wt %, about 10 wt % toabout 100 wt %, about 20 wt % to about 100 wt %, about 30 wt % to about100 wt %, about 40 wt % to about 100 wt %, about 50 wt % to about 100 wt%, about 60 wt % to about 100 wt %, about 70 wt % to about 100 wt %,about 80 wt % to about 100 wt %, or about 90 wt % to about 100 wt %, orwithin a range having any two of these values as endpoints, inclusive ofthe endpoints. In some embodiments, the protein can be a polylysine.

In some embodiments, the protein can have a lysine weight percentranging from about 0.5 wt % to about 20 wt %, including subranges. Forexample, the protein can have a lysine weight percent ranging from about0.5 wt % to about 20 wt %, about 1 wt % to about 19 wt %, about 2 wt %to about 18 wt %, about 3 wt % to about 17 wt %, about 4 wt % to about16 wt %, about 5 wt % to about 15 wt %, about 6 wt % to about 14 wt %,about 7 wt % to about 13 wt %, about 8 wt % to about 12 wt %, about 9 wt% to about 11 wt %, or about 9 wt % to about 10 wt %, or within a rangehaving any two of these values as endpoints, inclusive of the endpoints.In some embodiments, the protein can have a lysine weight percentranging from about 1 wt % to about 20 wt %. In some embodiments, theprotein can have a lysine weight percent ranging from about 5 wt % toabout 20 wt %. In some embodiments, the protein can have a lysine weightpercent ranging from about 1 wt % to about 12 wt %. In some embodiments,the protein can have a lysine weight percent ranging from about 5 wt %to about 12 wt %. In some embodiments, the protein can have a lysineweight percent ranging from about 1 wt % to about 15 wt %. In someembodiments, the protein can have a lysine weight percent ranging fromabout 5 wt % to about 15 wt %.

In some embodiments, the protein can be thermo-stable. In someembodiments, the protein can be non-thermo-stable. As described herein,protein thermo-stability is determined by a differential scanningcalorimetry (DSC), where a pre-dried protein powder (with moisture lessthan 3%) is scanned from 0° C. to 200° C. In the protein's DSC curves,an endothermic peak larger than 10 mW/mg is determined to be a“denaturation peak”, and the temperature corresponding to theendothermic “denaturation peak” is defined as the “denaturationtemperature” of the protein. A protein that is “thermo-stable” meansthat the protein has denaturation temperature of 200° C. or more. Forpurposes of the present disclosure, a protein with a denaturationtemperature below 200° C. is considered “non-thermo-stable.” Forexample, it was found that the whey from bovine milk listed in Table 1has a denaturation temperature at 158° C. according to DSC, andtherefore the whey is considered non-thermo-stable.

Protein Dissolution

In some embodiments, before blending with one or more polyurethanes, oneor more proteins can be dissolved in an aqueous solution to form anaqueous protein mixture. In some embodiments, dissolving the protein inan aqueous solution before blending the protein with one or morepolyurethanes can facilitate miscibility of the protein with the hardphase of the one or more polyurethanes. For example, dissolving theprotein in an aqueous solution before blending the protein with one ormore polyurethanes can facilitate miscibility of the protein with thehard phase of the polyurethane(s). Not all proteins are naturallymiscible with any phase of a polyurethane. For example, and asexemplified in Examples 33 and 34, casein is not necessarily misciblewith a polyurethane. As shown in these two examples, casein isimmiscible with L3360 if casein, water, and L3360 are mixed. Theobtained film had an opaque look with numerous optically visiblegranules in the film. However, casein is miscible with L3360's hardphase if casein is dissolved in a sodium hydroxide solution beforemixing with L3360. The film obtained by blending these components had atransparent and uniform look with no optically visible granules in thefilm.

Suitable aqueous solutions include, but are not limited to, water, anaqueous alkali solution, an aqueous acid solution, an aqueous solutionincluding an organic solvent, a urea solution, and mixtures thereof. Insome embodiments, the aqueous alkali solution can be a basic solutionsuch as a sodium hydroxide, ammonia or ammonium hydroxide solution. Insome embodiments, examples of an acidic aqueous solution can be anacetic acid or hydrochloric acid (HCl) solutions. Suitable organicsolvents include, but are not limited to, ethanol, isopropanol, acetone,ethyl acetate, isopropyl acetate, glycerol, and the like. In someembodiments, the protein concentration in the aqueous protein mixturecan range from about 10 g/L to about 300 g/L, including subranges. Forexample, the protein concentration in the aqueous protein mixture can beabout 10 g/L, about 20 g/L, about 30 g/L, about 40 g/L, about 50 g/L,about 60 g/L, about 70 g/L, about 80 g/L, about 90 g/L, about 100 g/L,about 150 g/L, about 200 g/L, about 250 g/L, or about 300 g/L, or withina range having any two of these values as endpoints, inclusive of theendpoints. In some embodiments, the protein concentration in the aqueousprotein mixture can range from about 10 g/L to about 300 g/L, about 20g/L to about 250 g/L, about 30 g/L to about 200 g/L, about 40 g/L toabout 150 g/L, about 50 g/L to about 100 g/L, about 60 g/L to about 90g/L, or about 70 g/L to about 80 g/L.

In some embodiments, the protein can be pretreated and/or purified toimprove solubility in water. Suitable pretreatments include, but are notlimited to, an acid treatment, an alkaline treatment, enzyme hydrolysis,and a salt treatment. An exemplary acid treatment is acid hydrolysiswith suitable acid such as acetic acid or HCl. An exemplary alkalinetreatment is alkaline hydrolysis with suitable base such as ammoniumhydroxide, NaOH, KOH, or a mixture thereof. Exemplary enzymes forhydrolysis include, but are not limited to, papain, bromelain, trypsin,alkaline proteases, and the like. Suitable purification treatmentsinclude, but are not limited to, removal of phytate with calcium salt,diafiltration, ultrafiltration, centrifugation, and the like.

In some embodiments, adding lysine or other hydrophilic amino acids tothe protein before blending with one or more polyurethanes canfacilitate miscibility of the protein with the hard phase of the one ormore polyurethanes.

Protein Hydrolysis

In some embodiments, the protein can be partially-hydrolyzed. Partialhydrolysis of the protein can promote dissolution of the protein inwater and/or facilitate miscibility of the protein with the hard phaseof the polyurethane. Partial-hydrolysis of the protein can beaccomplished using enzymes or strong to moderate base. Hydrolysis can befollowed by a reduction in viscosity and/or reduction in proteinmolecular weight. Characterization methods for determining a reductionin protein molecular weight, and thus a level of protein hydrolysis,include but are not limited to, light scattering, gel electrophoresis,size exclusion chromatography, solution viscosity measurement, terminalamino group detection with trinitrobenzene sulfonic acid or ninhydrin,or particle size measurement with laser diffraction. Example 21describes partially-hydrolyzed soy protein prepared using sodiumhydroxide according to some embodiments.

PEG-Modification of Proteins

In some embodiments, the protein can be chemically modified by covalentattachment of PEG polyethylene glycol (PEG) to the protein.PEG-modification of the protein can promote dissolution of the proteinin water and/or facilitate miscibility with the protein with the hardphase of the polyurethane. PEG-modification of a protein can beaccomplished using a method that covalently attaches hydrophilicpolyethylene glycol (PEG) chains to the protein.

In some embodiments, the amount of protein in the protein polyurethanealloy can range from about 10 wt % to about 50 wt % of protein,including subranges. For example, in some embodiments, the amount ofprotein in the protein polyurethane alloy range from about 10 wt % toabout 50 wt %, about 15 wt % to about 50 wt %, about 20 wt % to about 50wt %, about 25 wt % to about 50 wt %, about 30 wt % to about 50 wt %,about 35 wt % to about 50 wt %, about 40 wt % to about 50 wt %, about 45wt % to about 50 wt %, about 10 wt % to about 45 wt %, about 10 wt % toabout 40 wt %, about 10 wt % to about 35 wt %, about 10 wt % to about 30wt %, about 10 wt % to about 25 wt %, about 10 wt % to about 20, orabout 10 wt % to about 15%, or within a range having any two of thesevalues as endpoints, inclusive of the endpoints. In some embodiments,the amount of protein in the protein polyurethane alloy can range fromabout 20 wt % to about 35 wt %.

In some embodiments, the amount of polyurethane in the proteinpolyurethane alloy can range from about 50 wt % to about 90 wt %,including subranges. For example, in some embodiments, the amount ofpolyurethane in the protein polyurethane alloy can range from about 50wt % to about 90 wt %, about 55 wt % to about 90 wt %, about 60 wt % toabout 90 wt %, about 65 wt % to about 90 wt %, about 70 wt % to about 90wt %, about 75 wt % to about 90 wt %, about 80 wt % to about 90 wt %,about 85 wt % to about 90 wt %, about 50 wt % to about 85 wt %, about 50wt % to about 80 wt %, about 50 wt % to about 75 wt %, about 50 wt % toabout 70 wt %, about 50 wt % to about 65 wt %, about 50 wt % to about 60wt %, or about 50 wt % to about 55 wt %, or within a range having anytwo of these values as endpoints, inclusive of the endpoints. In someembodiments, the amount of polyurethane in the protein polyurethanealloy can range from about 65 wt % to about 80 wt %.

In some embodiments, the above-listed weight percent values and rangescan be based on the total weight of the protein polyurethane alloy orprotein polyurethane alloy layer. In some embodiments, the above-listedweight percent values and ranges can be based on the total weight ofonly protein and polyurethane in a protein polyurethane alloy or proteinpolyurethane alloy layer. Unless otherwise specified, a weight percentvalue or range for the polyurethane and the protein is based on thetotal weight of only protein and polyurethane in a protein polyurethanealloy or protein polyurethane alloy layer.

In some embodiments, the sum of the amount of protein plus the amount ofpolyurethane in the protein polyurethane alloy can be about 80 wt % ormore. For example, in some embodiments, the sum of the amount of proteinplus the amount of polyurethane in the protein polyurethane alloy canrange from about 80 wt % to 100 wt %, about 82 wt % to 100 wt %, about84 wt % to 100 wt %, about 86 wt % to 100 wt %, about 88 wt % to 100 wt%, about 90 wt % to 100 wt %, about 92 wt % to 100 wt %, about 94 wt %to 100 wt %, about 96 wt % to 100 wt %, or about 98 wt % to 100 wt %.

In some embodiments, the protein polyurethane alloy can include watermaking up a portion of the total weight percent of the material. In someembodiments, the amount of water in the protein polyurethane alloy canrange from about 1 wt % to about 10 wt %, including subranges. Forexample, in some embodiments, the amount of water in the proteinpolyurethane alloy can range from about 1 wt % to about 10 wt %, about 2wt % to about 10 wt %, about 3 wt % to about 10 wt %, about 4 wt % toabout 10 wt %, about 5 wt % to about 10 wt %, about 6 wt % to about 10wt %, about 7 wt % to about 10 wt %, about 8 wt % to about 10 wt %,about 1 wt % to about 9 wt %, about 1 wt % to about 8 wt %, about 1 wt %to about 7 wt %, about 1 wt % to about 6 wt %, about 1 wt % to about 5wt %, about 1 wt % to about 4 wt %, or about 1 wt % to about 3 wt %, orwithin a range having any two of these values as endpoints, inclusive ofthe endpoints.

A protein polyurethane alloy described herein can have one or more of(i) a second Dynamic Mechanical Analysis (DMA) modulus transition onsettemperature greater than the second DMA modulus transition onsettemperature of the unalloyed polyurethane (ii) a first DynamicMechanical Analysis (DMA) modulus transition onset temperaturesubstantially the same as the first DMA modulus transition onsettemperature of the unalloyed polyurethane, (iii) a DMA tan(δ) peak at atemperature substantially the same as the temperature of the DMA tan(δ)peak corresponding to the soft phase of the unalloyed polyurethane, (iv)a Young's modulus greater than the Young's modulus of the unalloyedpolyurethane, (v) a tensile strength greater than the tensile strengthof the unalloyed polyurethane, or (vi) a moisture vapor transmissionrate (MVTR) greater than the MVTR of the unalloyed polyurethane.

FIGS. 1-15 illustrate the effects of dissolving various amounts ofdifferent proteins in different polyurethanes to form polyurethanealloys according to some embodiments. Tables 3-6 list thermal andmechanical properties for various protein polyurethane alloys accordingto some embodiments, as well as thermal and mechanical properties forvarious polyurethanes. The samples tested were prepared by blending thelisted protein with an aqueous dispersion of the listed polyurethane,casting the mixture as a flat film, drying in oven at 45° C. overnight(16 to 24 hours), and conditioning at standard reference atmosphere (23°C., 50% humidity) for 24 hours before testing. The weight percent valuesin the figures and Tables 3-6 are the relative weight percent of solidsadded to the blend used to create the samples. For example, 0.825 gramsof gelatin and 5.5 g of L3360 (35 wt % solids) were blended to createthe sample for Example No. 9 having 30 wt % gelatin and 70 wt % L3360.The weight percentages in the figures and Tables 3-6 can closelyapproximate the weight percentages of protein and polyurethane in thedried samples of Example Nos. 1-44, based on the total weight of thedried samples. The dried samples included water making up a smallportion (for example, about 5% to about 10 wt %) of the total weightpercent of the sample.

Table 7 lists moisture vapor transmission rates for various proteinpolyurethane alloys according to some embodiments. The samples testedwere prepared as described in Example Nos. 45-56. The weight percentvalues in Table 7 are the relative weight percent of solids added to theblend used to create the samples. These weight percentages can closelyapproximate the weight percentages of protein and polyurethane in thedried samples of Example Nos. 45-56, based on the total weight of thedried samples. The dried samples included water making up a smallportion (for example, about 5% to about 10 wt %) of the total weightpercent of the sample.

The DMA temperatures in Tables 3 and 4 were measured using a DMA-850from TA Instruments. For testing, a 1 cm×2.5 cm strip was cut from asample film using a metal die. The cut film samples were loaded into thefilm and fiber tension clamp for testing. During testing, a pre-load of0.01 newtons (N) was applied to the cut film samples. The instrument wascooled to −80° C., held for 1 minute, then the temperature was ramped at4° C/minute to 200° C., or until the sample was too weak to be held intension. During the temperature ramp, the sample was oscillated 0.1%strain at a frequency of 1 Hz. The resulting storage modulus, lossmodulus, and tan(δ) values were plotted with temperature for each test.Unless otherwise specified, all DMA test data reported herein wasmeasured using this test methodology. The tensile strength values andYoung's modulus values in Tables 5 and 6 were measured according themethod provided by ASTM D638. The tensile strength values and Young'smodulus values are an average of at least three sample specimens tested.

The DMA graph shown in FIG. 1 shows the measured storage modulus (E′)for 100% L3360 (Example No. 1) and gelatin dissolved within L3360 atvarious weight percentages, namely 5 wt %, 10 wt %, 15 wt %, 20%, and 30wt % (Example Nos. 9 and 25-28). This graph illustrates that blendinggelatin with L3360 can create an alloy with a second DMA modulustransition onset temperature greater than the second DMA modulustransition onset temperature of 100% L3360. Without wishing to be boundby a particular theory, it is believed that as the hard phase comprisinggelatin and the hard segment of the polyurethane become continuous athigher gelatin content, the increase in the second DMA modulustransition onset temperature becomes more apparent in this test. Thistrend indicates that the gelatin is miscible with the hard phase ofL3360.

This miscibility of gelatin with the hard phase L3360 is furtherexemplified in the mechanical property graphs of FIG. 2 and FIG. 3,which compare two different mechanical properties of Example No. 1 andExample Nos. 9 and 25-28. As shown in FIG. 2, the maximum tensile stress(“tensile strength”) of the protein polyurethane alloys tested isgreater than the maximum tensile stress of 100% L3360. This increase inmaximum tensile stress is particularly significant at gelatin weightpercentages of 10 wt % or more. As shown in FIG. 3, the Young's modulusof the protein polyurethane alloys tested is greater than the Young'smodulus of 100% L3360. This increase in Young's modulus is particularlysignificant at gelatin weight percentages of 15 wt % or more.

The DMA graph shown in FIG. 4 shows the measured storage modulus (E′)for 100% L3360 (Example No. 1) and SPI dissolved within L3360 at variousweight percentages, namely 10 wt %, 20%, and 30 wt % (Example Nos. 21,30, and 31). This thermogram illustrates that blending SPI with L3360can create a protein polyurethane alloy with a second DMA modulustransition onset temperature greater than the second DMA modulustransition onset temperature of 100% L3360. As more SPI is added, theincrease in the second DMA modulus transition onset temperatureincreases. This trend indicates that the SPI in miscible with the hardphase of L3360.

This miscibility of SPI with the hard phase L3360 is further exemplifiedin the mechanical property graphs of FIG. 5 and FIG. 6, which comparetwo different mechanical properties of Example No. 1 and Example Nos.21, 30, and 31. As shown in FIG. 5, the maximum tensile stress (“tensilestrength”) of the protein polyurethane alloys tested is greater than themaximum tensile stress of 100% L3360. This increase in maximum tensilestress is particularly significant at SPI weight percentages of 10 wt %or more. As shown in FIG. 6, the Young's modulus of the proteinpolyurethane alloys tested is greater than the Young's modulus of 100%L3360. This increase in Young's modulus is particularly significant atSPI weight percentages of 15 wt % or more.

The DMA graph shown in FIG. 7 shows the measured storage modulus (E′)for 100% L3360 (Example No. 1) and various proteins dissolved withinL3360 at 30 wt % (Example Nos. 9 and 17-23). This graph illustrates thatgelatin, SPI, and other proteins can be blended with L3360 to create aprotein polyurethane alloy with a second DMA modulus transition onsettemperature greater than the second DMA modulus transition onsettemperature of 100% L3360. All the proteins, except Whey, producedprotein polyurethane alloys with a second DMA modulus transition onsettemperature greater than that of 100% L3360. It is believed Whey ismiscible with L3360's hard phase due to its ability to improvemechanical properties of a protein polyurethane alloy relative to 100%L3360. But it is believed that Whey did not increase the second DMAmodulus transition onset temperature because Whey has a low denaturationtemperature as determined by DSC.

Further, the graph of FIG. 7 shows that dissolving the various proteinswithin L3360 did not result in a protein polyurethane alloy having a DMAtransition temperature of the soft phase significantly different fromthe DMA transition temperature of the soft phase for 100% L3360. Asshown in Table 4, the Delta 1^(st) Modulus Transition Onset for all ofExample Nos. 9 and 17-23 was less than 10° C. Relatedly, the DeltaTan(δ) Peak Temperature for all of Example Nos. 9 and 17-23 was lessthan 10° C. These results indicate the proteins were not miscible withL3360's soft phase.

This selective miscibility of the proteins with the hard phase L3360 isfurther exemplified in the mechanical property test results plotted inthe graphs of FIG. 8A and FIG. 8B, and reported in Tables 5 and 6. Thegraphs of FIG. 8A and FIG. 8B compare the tensile strength and Young'smodulus of Example No. 1 and Example Nos. 9 and 17-23. An increase intensile strength and/or an increase in Young's modulus can indicate thata protein is miscible with the hard phase of L3360. Tables 5 and 6report the tensile strength and Young's modulus of the materials.

To further illustrate the selective miscibility of proteins with thehard phase of a polyurethane having both a soft phase and a hard phase,gelatin was blended with various exemplary polyurethanes. FIGS. 9-15show DMA thermograms for these exemplary blends as well as thermogramsfor the polyurethanes in the absence of gelatin. FIG. 9 compares the DMAdata for a protein polyurethane alloy made of 30 wt % gelatin and 70 wt% L3360 (Example No. 9) and 100% L3360 (Example No. 1). FIG. 10 comparesthe DMA data for a protein polyurethane alloy made of 30 wt % gelatinand 70 wt % HD-2001 (Example No. 15) and 100% HD-2001 (Example No. 7).FIG. 11 compares the DMA data for a protein polyurethane alloy made of30 wt % gelatin and 70 wt % Sancure (Example No. 14) and 100% Sancure(Example No. 6). FIG. 12 compares the DMA data for a proteinpolyurethane alloy made of 30 wt % gelatin and 70 wt % Impranil DLS(Example No. 12) and 100% Impranil DLS (Example No. 5). FIG. 13 comparesthe DMA data for a protein polyurethane alloy made of 30 wt % gelatinand 70 wt % UD-108 (Example No. 10) and 100% UD-108 (Example No. 2).FIG. 14 compares the DMA data for a protein polyurethane alloy made of30 wt % gelatin and 70 wt % UD-303 (Example No. 13) and 100% UD-303(Example No. 4). FIG. 15 compares the DMA data for a proteinpolyurethane alloy made of 30 wt % gelatin and 70 wt % UD-250 (ExampleNo. 11) and 100% UD-250 (Example No. 3).

FIG. 22 compares the DMA data for a protein polyurethane alloy made of30 wt % soy protein isolate (SPI) and 70 wt % IMPRAPERM® DL 5249 and a100% IMPRAPERM® DL 5249 polyurethane sample. Three samples of the 30 wt% soy protein isolate (SPI) and 70 wt % IMPRAPERM® DL 5249 alloy of FIG.22 having a mean thickness of 0.44 mm had an average Young's modulus of65.80 MPa. Three samples of the 100% IMPRAPERM® DL 5249 polyurethane ofFIG. 22 having a mean thickness of 0.7 mm had an average Young's modulusof 10.13 MPa. The DMA data shown in FIG. 22 and the results of thismechanical testing for the protein polyurethane alloy illustrate theselective miscibility of the SPI with the hard phase of IMPRAPERM® DL5249.

Tables 3 and 4 report DMA data for the various exemplary polyurethanesand those same polyurethanes blended with 30 wt % gelatin. Tables 5 and6 report the tensile strength and Young's modulus data for the variousexemplary polyurethanes and those same polyurethanes blended with 30 wt% gelatin. The results indicate selective miscibility of proteins testedwith the hard phase of polyurethanes tested.

In some embodiments, the protein polyurethane alloy can comprise apolyurethane having a second DMA modulus transition onset temperature inthe absence of protein. That same protein polyurethane alloy can have asecond DMA modulus transition onset temperature ranging from about 5° C.to about 100° C. greater than the second DMA modulus transition onsettemperature of the polyurethane in the absence of protein. This relativeincrease in the second DMA modulus transition onset temperature can bereferred to as “Delta 2^(nd) Modulus Transition Onset.” In someembodiments, the Delta 2^(nd) Modulus Transition Onset can be about 5°C. or more. In some embodiments, the Delta 2^(nd) Modulus TransitionOnset can range from about 5° C. to about 100° C., about 5° C. to about95° C., about 5° C. to about 90° C., about 5° C. to about 85° C., about5° C. to about 80° C., about 5° C. to about 75° C., about 5° C. to about70° C., about 5° C. to about 65° C., about 5° C. to about 60° C., about5° C. to about 55° C., about 5° C. to about 50° C., about 5° C. to about45° C., about 5° C. to about 40° C., about 5° C. to about 35° C., about5° C. to about 30° C., about 5° C. to about 25° C., about 5° C. to about20° C., about 5° C. to about 15° C., about 5° C. to about 10° C., about10° C. to about 100° C., about 15° C. to about 100° C., about 20° C. toabout 100° C., about 25° C. to about 100° C., about 30° C. to about 100°C., about 35° C. to about 100° C., about 40° C. to about 100° C., about45° C. to about 100° C., about 50° C. to about 100° C., about 55° C. toabout 100, about 60° C. to about 100° C., about 65° C. to about 100° C.,about 70° C. to about 100° C., about 75° C. to about 100° C., about 80°C. to about 100° C., about 85° C. to about 100° C., about 90° C. toabout 100° C., or about 95° C. to about 100° C., or within an rangehaving any two of these values as endpoints, inclusive of the endpoints.

In some embodiments, the Delta 2^(nd) Modulus Transition Onset can rangefrom about 5° C. to about 80° C. In some embodiments, the Delta 2^(nd)Modulus Transition Onset can range from about 20° C. to about 80° C. Insome embodiments, the Delta 2^(nd) Modulus Transition Onset can rangefrom about 40° C. to about 80° C. In some embodiments, the Delta 2^(nd)Modulus Transition Onset can be greater than about 100° C. For example,the Delta 2^(nd) Modulus Transition Onset can range from about 100° C.to about 150° C.

In some embodiments, a soy protein polyurethane alloy can comprise apolyurethane having a second DMA modulus transition onset temperature inthe absence of soy protein. That same soy protein polyurethane alloy canhave a second DMA modulus transition onset temperature ranging fromabout 15° C. to about 100° C. greater than the second DMA modulustransition onset temperature of the polyurethane in the absence of soyprotein. In some embodiments, the Delta 2^(nd) Modulus Transition Onsetfor the soy protein polyurethane alloy can be about 15° C. or more. Insome embodiments, the Delta 2^(nd) Modulus Transition Onset for a soyprotein polyurethane alloy can range from about 15° C. to about 100° C.,about 15° C. to about 95° C., about 15° C. to about 90° C., about 15° C.to about 85° C., about 15° C. to about 80° C., about 15° C. to about 75°C., about 15° C. to about 70° C., about 15° C. to about 65° C., about15° C. to about 60° C., about 15° C. to about 55° C., about 15° C. toabout 50° C., about 15° C. to about 45° C., about 15° C. to about 40°C., about 15° C. to about 35° C., about 15° C. to about 30° C., about15° C. to about 25° C., about 15° C. to about 20° C., about 20° C. toabout 100° C., about 25° C. to about 100° C., about 30° C. to about 100°C., about 35° C. to about 100° C., about 40° C. to about 100° C., about45° C. to about 100° C., about 50° C. to about 100° C., about 55° C. toabout 100, about 60° C. to about 100° C., about 65° C. to about 100° C.,about 70° C. to about 100° C., about 75° C. to about 100° C., about 80°C. to about 100° C., about 85° C. to about 100° C., about 90° C. toabout 100° C., or about 95° C. to about 100° C., or within an rangehaving any two of these values as endpoints, inclusive of the endpoints.

In some embodiments, the protein polyurethane alloy can have a secondDMA modulus transition onset temperature ranging from about 100° C. toabout 200° C., including subranges. For example, in some embodiments,the protein polyurethane alloy can have a second DMA modulus transitiononset temperature ranging from about 100° C. to about 200° C., about100° C. to about 195° C., about 100° C. to about 190° C., about 100° C.to about 185° C., about 100° C. to about 180° C., about 100° C. to about175° C., about 100° C. to about 170° C., about 100° C. to about 165° C.,about 100° C. to about 160° C., about 100° C. to about 155° C., about100° C. to about 150° C., about 100° C. to about 145° C., about 100° C.to about 140° C., about 100° C. to about 135° C., about 100° C. to about130° C., about 100° C. to about 125° C., or about 100 to about 120° C.,about 105° C. to about 200° C., about 110° C. to about 200° C., about115° C. to about 200° C., about 120° C. to about 200° C., about 125° C.to about 200° C., about 130° C. to about 200° C., about 135° C. to about200° C., about 140° C. to about 200° C., about 145° C. to about 200° C.,about 150° C. to about 200° C., about 155° C. to about 200° C., about160° C. to about 200° C., about 165° C. to about 200° C., about 170° C.to about 200° C., about 175° C. to about 200° C., or about 180° C. toabout 200° C., or within a range having any two of these values asendpoints, inclusive of the endpoints. In some embodiments, the proteinpolyurethane alloy can have a second DMA modulus transition onsettemperature ranging from about 120° C. to about 200° C. In someembodiments, the protein polyurethane alloy can have a second DMAmodulus transition onset temperature ranging from about 130° C. to about200° C. In some embodiments, the protein polyurethane alloy can have asecond DMA modulus transition onset temperature ranging from about 165°C. to about 200° C.

In some embodiments, the soy protein polyurethane alloy can have asecond DMA modulus transition onset temperature ranging from about 130°C. to about 200° C., including subranges. For example, in someembodiments, the soy protein polyurethane alloy can have a second DMAmodulus transition onset temperature ranging from about 130° C. to about200° C., about 130° C. to about 195° C., about 130° C. to about 190° C.,about 130° C. to about 185° C., about 130° C. to about 180° C., about130° C. to about 175° C., about 130° C. to about 170° C., about 130° C.to about 165° C., about 130° C. to about 160° C., about 130° C. to about155° C., about 130° C. to about 150° C., about 130° C. to about 145° C.,about 130° C. to about 140° C., about 135° C. to about 200° C., about140° C. to about 200° C., about 145° C. to about 200° C., about 150° C.to about 200° C., about 155° C. to about 200° C., about 160° C. to about200° C., about 165° C. to about 200° C., about 170° C. to about 200° C.,about 175° C. to about 200° C., about 180° C. to about 200° C., about185° C. to about 200° C., or about 190° C. to about 200° C., or within arange having any two of these values as endpoints, inclusive of theendpoints.

In some embodiments, the protein polyurethane alloy can have a first DMAmodulus transition temperature below 30° C. In some embodiments, theprotein polyurethane alloy can have a first DMA modulus transition onsettemperature ranging from about −65° C. to about 30° C., includingsubranges. For example, in some embodiments, the first DMA modulustransition onset temperature for the protein polyurethane alloy canrange from about −65° C. to about 30° C., about −65° C. to about 25° C.,about −65° C. to about 20° C., about −65° C. to about 15° C., about −65°C. to about 10° C., about −65° C. to about 5° C., about −65° C. to about1° C., about −65° C. to 0° C., about −65° C. to about 1° C., about −65°C. to about −5° C., about −65° C. to about −10° C. , about −65° C. toabout −15° C. , about −65° C. to about −20° C. , about −65° C. to about−25° C., about −65° C. to about −30° C., about −65° C. to about −35° C.,about −65° C. to about −35° C., about −65° C. to about −40° C., or about−65° C. to about −45° C., or within a range having any two of thesevalues as endpoints, inclusive of the end points.

In some embodiments, the protein polyurethane alloy can comprise apolyurethane having a first DMA modulus transition onset temperature inthe absence of protein. That same protein polyurethane alloy can have afirst DMA modulus transition onset temperature that is +/−X ° C. thefirst DMA modulus transition onset temperature of the polyurethane inthe absence of protein. This relative increase or decrease in the firstDMA modulus transition onset temperature can be referred to as “Delta1^(st) Modulus Transition Onset.” In some embodiments, X can be 1, 2, 3,4, 5, 6, 7, 8, 9, or 10.

In some embodiments, the protein polyurethane alloy can have a DMAtan(δ) peak temperature below 30° C. In some embodiments, the proteinpolyurethane alloy can have a DMA tan(δ) peak temperature ranging fromabout −60° C. to about 30° C., including subranges. For example, in someembodiments, the DMA tan(δ) peak temperature for the proteinpolyurethane alloy can range from about −60° C. to about 30° C., about−60° C. to about 25° C., about −60° C. to about 20° C., about −60° C. toabout 15° C., about −60° C. to about 10° C., about −60° C. to about 5°C., about −60° C. to about 1° C., about −60° C. to 0° C., about −60° C.to about 1° C., about −60° C. to about −5° C., about −60° C. to about−10° C. , about −60° C. to about −15° C. , about −60° C. to about −20°C. , about −60° C. to about −25° C., about −60° C. to about −30° C.,about −60° C. to about −35° C., or about −60° C. to about −40° C., orwithin a range having any two of these values as endpoints.

In some embodiments, the protein polyurethane alloy can include apolyurethane having a DMA tan(δ) peak temperature corresponding to thesoft phase of the polyurethane in the absence of protein. That same theprotein polyurethane alloy can have a DMA tan(δ) peak temperature thatis +/−Y° C. the DMA tan(δ) peak temperature corresponding to the softphase of the polyurethane in the absence of protein. This relativeincrease or decrease in the DMA tan(δ) peak temperature can be referredto as “Delta Tan(δ) Peak Temperature.” In some embodiments, Y can be 1,2, 3, 4, 5, 6, 7, 8, 9, or 10.

In some embodiments, the protein polyurethane alloy can comprise apolyurethane having a tensile strength in the absence of protein. Thatsame protein polyurethane alloy can have a tensile strength about 5% toabout 55% greater than the tensile strength of the polyurethane in theabsence of protein. This relative percent increase in tensile strengthcan be referred to as “% Delta Tensile Strength.” In some embodiments, %Delta Tensile Strength can be 5% or more. In some embodiments, % DeltaTensile Strength can range from about 5% to about 55%, about 10% toabout 55%, about 15% to about 55%, about 20% to about 55%, about 25% toabout 55%, about 30% to about 55%, about 35% to about 55%, about 40% toabout 55%, about 45% to about 55%, about 50% to about 55%, about 5% toabout 50%, about 5% to about 45%, about 5% to about 40%, about 5% toabout 35%, about 5% to about 30%, about 5% to about 25%, about 5% toabout 20%, about 5% to about 15%, or about 5% to about 10%, or within arange having any two of these values as endpoints, inclusive of theendpoints. In some embodiments, % Delta Tensile Strength can range fromabout 15% to about 55%. In some embodiments, % Delta Tensile Strengthcan be greater than about 55%. For example, % Delta Tensile Strength canrange from about 55% to about 1000%.

In some embodiments, the soy protein polyurethane alloy can comprise apolyurethane having a tensile strength in the absence of soy protein.That same soy protein polyurethane alloy can have a tensile strengthabout 10% to about 45% greater than the tensile strength of thepolyurethane in the absence of soy protein. In some embodiments, % DeltaTensile Strength for the soy protein polyurethane alloy can be 10% ormore. In some embodiments, % Delta Tensile Strength for the soy proteinpolyurethane alloy can range from about 10% to about 45%, about 15% toabout 45%, about 20% to about 45%, about 25% to about 45%, about 30% toabout 45%, about 35% to about 45%, about 40% to about 45%, about 10% toabout 40%, about 10% to about 35%, about 10% to about 30%, about 10% toabout 25%, about 10% to about 20%, or about 10% to about 15%, or withina range having any two of these values as endpoints, inclusive of theendpoints.

In some embodiments, the protein polyurethane alloy can comprise apolyurethane having a tensile strength in the absence of protein. Thatsame protein polyurethane alloy can have a tensile strength ranging fromabout 2 MPa (megapascals) to about 8 MPa greater than the tensilestrength of the polyurethane in the absence of protein. This relativeincrease in tensile strength can be referred to as “Delta TensileStrength.” In some embodiments, Delta Tensile Strength can be 2 MPa ormore. In some embodiments, Delta Tensile Strength can range from about 2MPa to about 8 MPa, about 3 MPa to about 8 MPa, about 4 MPa to about 8MPa, about 5 MPa to about 8 MPa, about 6 MPa to about MPa, about 7 MPato about 8 MPa, about 2 MPa to about 7 MPa, about 2 MPa to about 6 MPa,about 2 MPa to about 5 MPa, about 2 MPa to about 4 MPa, or about 2 MPato about 3 MPa, or within a range having any two of these values asendpoints, inclusive of the endpoints. In some embodiments, DeltaTensile Strength can range from about 5 MPa to about 8 MPa. In someembodiments, Delta Tensile Strength can be greater than about 8 MPa. Forexample, Delta Tensile Strength can range from about 8 MPa to about 15MPa.

In some embodiments, the soy protein polyurethane alloy can comprise apolyurethane having a tensile strength in the absence of soy protein.That same soy protein polyurethane alloy can have a tensile strengthranging from about 1.5 MPa to about 5.5 MPa greater than the tensilestrength of the polyurethane in the absence of soy protein. In someembodiments, Delta Tensile Strength for the soy protein polyurethanealloy can be 1.5 MPa or more. In some embodiments, Delta TensileStrength for the soy protein polyurethane alloy can range from about 1.5MPa to about 5.5 MPa, about 2 MPa to about 5.5 MPa, about 3 MPa to about5.5 MPa, about 4 MPa to about 5.5 MPa, about 1.5 MPa to about 5 MPa,about 1.5 MPa to about 4 MPa, or about 1.5 MPa to about 3 MPa, or withina range having any two of these values as endpoints, inclusive of theendpoints.

In some embodiments, the protein polyurethane alloy can have a tensilestrength ranging from about 7MPa to about 21 MPa, including subranges.For example, in some embodiments, the protein polyurethane alloy canhave a tensile strength ranging from about 7 MPa to about 21 MPa, about10 MPa to about 21 MPa, about 15 MPa to about 21 MPa, about 7MPa toabout 15 MPa, or about 7MPa to about 10 MPa, or within a range havingany of these values as endpoints, inclusive of the endpoints. In someembodiments, the protein polyurethane alloy can have a tensile strengthgreater than about 21 MPa. For example, the protein polyurethane alloycan have a tensile strength ranging from about 21 MPa to about 25 MPa.

In some embodiments, the soy protein polyurethane alloy can have atensile strength ranging from about 14 MPa to about 19 MPa or about 16MPa to about 19 MPa.

In some embodiments, the polyurethane in the absence of protein can havea tensile strength of about 2 MPa or more. In some embodiments, thepolyurethane in the absence of protein can have a tensile strengthranging from about 2 MPa to about 35 MPa, including subranges. Forexample, in some embodiments, the polyurethane in the absence of proteincan have a tensile strength ranging from about 2 MPa to about 35 MPa,about 5MPa to about 30 MPa, about 10 MPa to about 25 MPa, or about 15MPa to about 20 MPa, or within a range having any two of these values asendpoints, inclusive of the endpoints. In some embodiments, thepolyurethane in the absence of protein can have a tensile strengthranging from about 10 MPa to about 15 MPa. In some embodiments, thepolyurethane in the absence of protein can have a tensile strengthranging from about 1 MPa to about 35 MPa.

In some embodiments, the protein polyurethane alloy can comprise apolyurethane having a Young's modulus in the absence of protein. Thatsame protein polyurethane alloy can have a Young's modulus ranging fromabout 10% to about 600% greater than the Young's modulus of thepolyurethane in the absence of protein. This relative percent increasein Young's modulus can be referred to as “% Delta Young's Modulus.” Insome embodiments, the % Delta Young's Modulus can be about 10% or more.In some embodiments, the % Delta Young's Modulus can range from about10% to about 600%, about 20% to about 600%, about 30% to about 600%,about 40% to about 600%, about 50% to about 600%, about 60% to about600%, about 70% to about 600%, about 80% to about 600%, about 90% toabout 600%, about 100% to about 600%, about 200% to about 600%, about300% to about 600%, about 400% to about 600%, or about 500% to about600%, or within a range having any two of these values as endpoints,inclusive of the end points. In some embodiments, the % Delta Young'sModulus can range from about 40% to about 600%. In some embodiments, the% Delta Young's Modulus can greater than about 600%. For example, the %Delta Young's Modulus can range from about 600% to about 2400%.

In some embodiments, the soy protein polyurethane alloy can comprise apolyurethane having a Young's modulus in the absence of soy protein.That same soy protein polyurethane alloy can have a Young's modulusranging from about 60% to about 570% greater than the Young's modulus ofthe polyurethane in the absence of soy protein. In some embodiments, the% Delta Young's Modulus for the soy protein polyurethane alloy can beabout 60% or more. In some embodiments, the % Delta Young's Modulus forthe soy protein polyurethane alloy can range from about 60% to about570%, about 100% to about 570%, about 200% to about 570%, about 300% toabout 570%, about 400% to about 570%, or about 500% to about 570%, orwithin a range having any two of these values as endpoints, inclusive ofthe end points.

In some embodiments, the protein polyurethane alloy can comprise apolyurethane having a Young's modulus in the absence of protein. Thatsame protein polyurethane alloy can have a Young's modulus ranging fromabout 10 MPa to about 350 MPa greater than the Young's modulus of thepolyurethane in the absence of protein. This relative increase inYoung's modulus can be referred to as “Delta Young's Modulus.” In someembodiments, the Delta Young's Modulus can be greater than 10 MPa. Insome embodiments, the Delta Young's Modulus can range from about 10 MPato about 350 MPa, about 25 MPa to about 350 MPa, about 50 MPa to about350 MPa, about 100 MPa to about 350 MPa, about 150 MPa to about 350 MPa,about 200 MPa to about 350 MPa, about 250 MPa to about 350 MPa, about300 MPa to about 350 MPa, about 10 MPa to about 300 MPa, about 10 MPa toabout 250 MPa, about 10 MPa to about 200 MPa, about 10 MPa to about 150MPa, about 10 MPa to about 100 MPa, about 10 MPa to about 50 MPa, orabout 10 MPa to about 25 MPa, or within a range having any two of thesevalues as endpoints, inclusive of the endpoints. In some embodiments,the Delta Young's Modulus can range from about 25 MPa to about 350 MPa.In some embodiments, the Delta Young's Modulus can range from about 100MPa to about 350 MPa.

In some embodiments, the soy protein polyurethane alloy can comprise apolyurethane having a Young's modulus in the absence of soy protein.That same soy protein polyurethane alloy can have a Young's modulusranging from about 35 MPa to about 340 MPa greater than the Young'smodulus of the polyurethane in the absence of soy protein. In someembodiments, the Delta Young's Modulus for the soy protein polyurethanealloy can be greater than 35 MPa. In some embodiments, the Delta Young'sModulus for the soy protein polyurethane alloy can range from about 35MPa to about 340 MPa, about 50 MPa to about 340 MPa, about 100 MPa toabout 340 MPa, about 150 MPa to about 340 MPa, about 200 MPa to about340 MPa, about 250 MPa to about 340 MPa, about 300 MPa to about 340 MPa,about 35 MPa to about 300 MPa, about 35 MPa to about 250 MPa, about 35MPa to about 200 MPa, about 35 MPa to about 150 MPa, about 35 MPa toabout 100 MPa, or about 35 MPa to about 50 MPa, or within a range havingany two of these values as endpoints, inclusive of the endpoints.

In some embodiments, the protein polyurethane alloy can have a Young'smodulus ranging from about 50 MPa to about 450 MPa, including subranges.For example, in some embodiments, the protein polyurethane alloy canhave a Young's modulus ranging from about 50 MPa to about 450 MPa, about75 MPa to about 450 MPa, about 100 MPa to about 450 MPa, about 150 MPato about 450 MPa, about 200 MPa to about 450 MPa, about 250 MPa to about450 MPa, about 300 MPa to about 450 MPa, about 350 MPa to about 450 MPa,about 400 MPa to about 450 MPa, about 50 MPa to about 400 MPa, about 50MPa to about 350 MPa, about 50 MPa to about 300 MPa, about 50 MPa toabout 250 MPa, about 50 MPa to about 200 MPa, about 50 MPa to about 150MPa, about 50 MPa to about 100 MPa, or about 50 MPa to about 75 MPa, orwithin a range having any two of these values as endpoints, inclusive ofthe endpoints. In some embodiments, the protein polyurethane alloy canhave a Young's modulus ranging from about 75 MPa to about 450 MPa. Insome embodiments, the protein polyurethane alloy can have a Young'smodulus greater than about 450 MPa. For example, the proteinpolyurethane alloy can have a Young's modulus ranging from about 450 MPato about 580 MPa.

In some embodiments, the soy protein polyurethane alloy can have aYoung's modulus ranging from about 90 MPa to about 400 MPa, includingsubranges. For example, in some embodiments, the soy proteinpolyurethane alloy can have a Young's modulus ranging from about 90 MPato about 400 MPa, about 100 MPa to about 400 MPa, about 150 MPa to about400 MPa, about 200 MPa to about 400 MPa, about 250 MPa to about 400 MPa,about 300 MPa to about 400 MPa, about 350 MPa to about 400 MPa, about 90MPa to about 350 MPa, about 90 MPa to about 300 MPa, about 90 MPa toabout 250 MPa, about 90 MPa to about 200 MPa, about 90 MPa to about 150MPa, or about 90 MPa to about 100 MPa, or within a range having any twoof these values as endpoints, inclusive of the endpoints.

In some embodiments, the polyurethane in the absence of protein can havea Young's modulus of about 10 MPa or more. In some embodiments, thepolyurethane in the absence of protein can have a Young's modulusranging from about 10 MPa to about 600 MPa, including subranges. Forexample, in some embodiments, the polyurethane in the absence of proteincan have a Young's modulus ranging from about 10 MPa to about 600 MPa,about 10 MPa to about 500 MPa, about 10 MPa to about 400 MPa, about 10MPa to about 300 MPa, about 10 MPa to about 200 MPa, about 10 MPa toabout 100 MPa, or about 10 MPa to about 50 MPa, or within a range havingany two of these values as endpoints, inclusive of the endpoints. Insome embodiments, the polyurethane in the absence of protein can have aYoung's modulus ranging from about 50 MPa to about 100 MPa.

In some embodiments, the protein polyurethane alloy can comprise apolyurethane having a moisture vapor transmission rate in the absence ofthe protein. That same protein polyurethane alloy can have a moisturevapor transmission rate about 20% or more greater than the moisturevapor transmission rate in the absence of the protein. In someembodiments, the protein polyurethane alloy can have a moisture vaportransmission rate about 20% to about 600% greater than the moisturevapor transmission rate of the polyurethane in the absence of protein.This relative percent increase in moisture vapor transmission rate canbe referred to as “% Delta MVTR.” In some embodiments, % Delta MVTR canbe about 20% or more. In some embodiments, % Delta MVTR can range fromabout 20% to about 600%, about 30% to about 600%, about 40% to about600%, about 50% to about 600%, about 75% to about 600%, about 100% toabout 600%, about 125% to about 600%, about 150% to about 600%, about200% to about 600%, about 20% to about 500%, about 20% to about 400%,about 20% to about 300%, about 20% to about 200%, about 20% to about150%, about 20% to about 125%, or about 20% to about 100%, or within arange having any two of these values as endpoints, inclusive of theendpoints.

In some embodiments, the soy protein polyurethane alloy can comprise a %Delta MVTR of about 20% or more. In some embodiments, % Delta MVTR forthe soy protein polyurethane alloy can range from about 20% to about600%, about 30% to about 600%, about 40% to about 600%, about 50% toabout 600%, about 75% to about 600%, about 100% to about 600%, about125% to about 600%, about 150% to about 600%, about 200% to about 600%,about 20% to about 500%, about 20% to about 400%, about 20% to about300%, about 20% to about 200%, about 20% to about 150%, about 20% toabout 125%, or about 20% to about 100%, or within a range having any twoof these values as endpoints, inclusive of the endpoints.

In some embodiments, the protein polyurethane alloy can comprise apolyurethane having a moisture vapor transmission rate in the absence ofprotein. That same protein polyurethane alloy can comprise a moisturevapor transmission rate ranging from about 30 g/m²/24 hr to about 500g/m²/24 hr greater than the moisture vapor transmission rate of thepolyurethane in the absence of protein. This relative increase inmoisture vapor transmission rate can be referred to as “Delta MVTR.” Insome embodiments, the Delta MVTR can be greater than or equal to 30g/m²/24 hr. In some embodiments, the Delta MVTR can range from about 30g/m²/24 hr to about 500 g/m²/24 hr, about 40 g/m²/24 hr to about 500g/m²/24 hr, about 50 g/m²/24 hr to about 500 g/m²/24 hr, about 75g/m²/24 hr to about 500 g/m²/24 hr, about 100 g/m²/24 hr to about 500g/m²/24 hr, about 150 g/m²/24 hr to about 500 g/m²/24 hr, about 200g/m²/24 hr to about 500 g/m²/24 hr, about 300 g/m²/24 hr to about 500g/m²/24 hr, about 30 g/m²/24 hr to about 400 g/m²/24 hr, about 30g/m²/24 hr to about 300 g/m²/24 hr, about 30 g/m²/24 hr to about 200g/m²/24 hr, about 30 g/m²/24 hr to about 150 g/m²/24 hr, about 30g/m²/24 hr to about 100 g/m²/24 hr, about 30 MPa to about 75 g/m²/24 hr,or about 30 g/m²/24 hr to about 50 g/m²/24 hr, or within a range havingany two of these values as endpoints, inclusive of the endpoints.

In some embodiments, the soy protein polyurethane alloy can comprise aDelta MVTR greater than or equal to 30 g/m²/24 hr. In some embodiments,the Delta MVTR for the soy protein polyurethane alloy can range fromabout 30 g/m²/24 hr to about 500 g/m²/24 hr, about 40 g/m²/24 hr toabout 500 g/m²/24 hr, about 50 g/m²/24 hr to about 500 g/m²/24 hr, about75 g/m²/24 hr to about 500 g/m²/24 hr, about 100 g/m²/24 hr to about 500g/m²/24 hr, about 150 g/m²/24 hr to about 500 g/m²/24 hr, about 200g/m²/24 hr to about 500 g/m²/24 hr, about 300 g/m²/24 hr to about 500g/m²/24 hr, about 30 g/m²/24 hr to about 400 g/m²/24 hr, about 30g/m²/24 hr to about 300 g/m²/24 hr, about 30 g/m²/24 hr to about 200g/m²/24 hr, about 30 g/m²/24 hr to about 150 g/m²/24 hr, about 30g/m²/24 hr to about 100 g/m²/24 hr, about 30 MPa to about 75 g/m²/24 hr,or about 30 g/m²/24 hr to about 50 g/m²/24 hr, or within a range havingany two of these values as endpoints, inclusive of the endpoints.

In some embodiments, the protein polyurethane alloy can comprise amoisture vapor transmission rate ranging from about 30 g/m²/24 hr toabout 1000 g/m²/24 hr, including subranges. For example, in someembodiments, the protein polyurethane alloy can comprise a moisturevapor transmission rate ranging from about 30 g/m²/24 hr to about 1000g/m²/24 hr, about 60 g/m²/24 hr to about 1000 g/m²/24 hr, about 100g/m²/24 hr to about 1000 g/m²/24 hr, about 200 g/m²/24 hr to about 1000g/m²/24 hr, about 250 g/m²/24 hr to about 1000 g/m²/24 hr, about 300g/m²/24 hr to about 1000 g/m²/24 hr, about 400 g/m²/24 hr to about 1000g/m²/24 hr, about 500 g/m²/24 hr to about 1000 g/m²/24 hr, about 30g/m²/24 hr to about 900 g/m²/24 hr, about 30 g/m²/24 hr to about 800g/m²/24 hr, about 30 g/m²/24 hr to about 700 g/m²/24 hr, about 30g/m²/24 hr to about 600 g/m²/24 hr, about 30 g/m²/24 hr to about 500g/m²/24 hr, about 30 g/m²/24 hr to about 400 g/m²/24 hr, about 30g/m²/24 hr to about 300 g/m²/24 hr, about 30 g/m²/24 hr to about 250g/m²/24 hr, about 30 g/m²/24 hr to about 200 g/m²/24 hr, or about 30g/m²/24 hr to about 100 g/m²/24 hr, or within a range having any two ofthese values as endpoints, inclusive of the endpoints. In someembodiments, the protein polyurethane alloy can comprise a moisturevapor transmission rate of greater than or equal to about 250 g/m²/24hr. For example, in some embodiments, the protein polyurethane alloy cancomprise a moisture vapor transmission rate ranging from about 250g/m²/24 hr to about 1000 g/m²/24 hr, about 250 g/m²/24 hr to about 700g/m²/24 hr, or about 250 g/m²/24 hr to about 500 g/m²/24 hr.

In some embodiments, the soy protein polyurethane alloy can comprise amoisture vapor transmission rate ranging from about 30 g/m²/24 hr toabout 1000 g/m²/24 hr, including subranges. For example, in someembodiments, the soy protein polyurethane alloy can comprise a moisturevapor transmission rate ranging from about 30 g/m²/24 hr to about 1000g/m²/24 hr, about 60 g/m²/24 hr to about 1000 g/m²/24 hr, about 100g/m²/24 hr to about 1000 g/m²/24 hr, about 200 g/m²/24 hr to about 1000g/m²/24 hr, about 250 g/m²/24 hr to about 1000 g/m²/24 hr, about 300g/m²/24 hr to about 1000 g/m²/24 hr, about 400 g/m²/24 hr to about 1000g/m²/24 hr, about 500 g/m²/24 hr to about 1000 g/m²/24 hr, about 30g/m²/24 hr to about 900 g/m²/24 hr, about 30 g/m²/24 hr to about 800g/m²/24 hr, about 30 g/m²/24 hr to about 700 g/m²/24 hr, about 30g/m²/24 hr to about 600 g/m²/24 hr, about 30 g/m²/24 hr to about 500g/m²/24 hr, about 30 g/m²/24 hr to about 400 g/m²/24 hr, about 30g/m²/24 hr to about 300 g/m²/24 hr, about 30 g/m²/24 hr to about 250g/m²/24 hr, about 30 g/m²/24 hr to about 200 g/m²/24 hr, or about 30g/m²/24 hr to about 100 g/m²/24 hr, or within a range having any two ofthese values as endpoints, inclusive of the endpoints. In someembodiments, the soy protein polyurethane alloy can comprise a moisturevapor transmission rate of greater than or equal to about 250 g/m²/24hr. For example, in some embodiments, the soy protein polyurethane alloycan comprise a moisture vapor transmission rate ranging from about 250g/m²/24 hr to about 1000 g/m²/24 hr, about 250 g/m²/24 hr to about 700g/m²/24 hr, or about 250 g/m²/24 hr to about 500 g/m²/24 hr.

FIG. 17 shows a layered material 1700 according to some embodiments.Layered material 1700 includes a polyurethane protein alloy layer 1720attached to a substrate layer 1710. Polyurethane protein alloy layer1720 can be directly attached to a surface of substrate layer 1710 orattached to a surface of substrate layer 1710 via an intermediate layer,for example an adhesive layer. Direct attachment can be achieved using,for example, a thermal bonding process or a stitching. Polyurethaneprotein alloy layer 1720 can be referred to as a “first polyurethaneprotein alloy layer.”

Polyurethane protein alloy layer 1720 can include one or more types ofprotein and one or more polyurethanes. In some embodiments, polyurethaneprotein alloy layer 1720 can include one or more proteins dissolvedwithin one or more polyurethanes. In some embodiments, polyurethaneprotein alloy layer 1720 can be transparent. The transparency of apolyurethane protein alloy layer is evaluated before dying or otherwisecoloring a polyurethane protein alloy layer.

A transparent protein polyurethane alloy layer can provide uniquecharacteristics for a layered material. For example, compared to anon-transparent layer, a transparent protein polyurethane alloy layercan provide unique depth of color when dyed. Likewise, a transparentprotein polyurethane alloy layer can provide its mechanical propertiesto a layered material without significantly influencing the aestheticproperties of the material.

Protein polyurethane alloy layer 1720 includes a bottom surface 1722, atop surface 1724, and thickness 1726 measured between bottom surface1722 and top surface 1724. In some embodiments, thickness 1726 can rangefrom about 25 microns to about 400 microns (micrometers, μm), includingsubranges. For example, thickness 1726 can be about 25 microns, about 50microns, about 100 microns, about 125 microns, about 150 microns, about175 microns, about 200 microns, about 250 microns, about 300 microns,about 350 microns, or about 400 microns, or within a range having anytwo of these values as endpoints, inclusive of the endpoints. In someembodiments, thickness 1726 can range from about 50 microns to about 350microns, about 75 microns to about 300 microns, about 100 microns toabout 250 microns, about 125 microns to about 200 microns, or about 150microns to about 175 microns.

Protein polyurethane alloy layer 1720 can have a dry weight, measured ingrams per square meter (gsm, g/m²), ranging from about 25 g/m² to about125 g/m², including subranges. For example, protein polyurethane alloylayer 1720 can have a dry weight of about 25 g/m², about 50 g/m², about75 g/m², about 100 g/m², or about 125 g/m², or within a range having anytwo of these values as endpoints, inclusive of the endpoints. In someembodiments, protein polyurethane alloy layer 1720 can have a dry weightranging from about 25 g/m² to about 125 g/m², about 25 g/m² to about 100g/m², or about 50 g/m² to about 100 g/m².

Unless specified otherwise, the dry weight of a layer is measured duringthe process of making a material using the following method. First,before applying the layer in question to the material, a first sample(about 10 centimeters in diameter) of the material is cut, and theweight and dimensions are measured to calculate a first dry weight. If asacrificial layer is present, it is removed before measuring the weightand dimensions. Second, after applying and drying the layer in question,a second sample of the same size is cut from the material, and theweight and dimensions are measured to calculate a second dry weight. Ifa sacrificial layer is present, it is removed before measuring theweight and dimensions. Third, the first dry weight is subtracted fromthe second dry weight to obtain the dry weight of the layer in question.All the weight and dimension measurements are performed at the samehumidity level, typically the humidity level of the manufacturingenvironment in which the material is made. For purposes of calculating adry weight, three separate dry weight tests are performed, and theaverage dry weight is reported as the dry weight of the layer.

In some embodiments, protein polyurethane alloy layer 1720 can be anon-foamed layer. A “non-foamed” layer means a layer having a density,measured in the percent void space for the layer, of 5% void space orless, for example 0% void space to 5% void space. In some embodiments,protein polyurethane alloy layer 1720 can be a foamed layer. In suchembodiments, protein polyurethane alloy layer 1720 can have a density,measured in the percent void space for layer 1720, ranging from about 5%void space to about 70% void space, including subranges. For example,protein polyurethane alloy layer 1720 can have about 5% void space,about 10% void space, about 20% void space, about 30% void space, about35% void space, about 40% void space, about 45% void space, about 50%void space, about 55% void space, about 60% void space, about 65% voidspace, or about 70% void space, or within a range having any two ofthese values as endpoints, inclusive of the endpoints. In someembodiments, protein polyurethane alloy layer 1720 can have a percentvoid space ranging from about 10% to about 65%, about 20% to about 60%,about 30% to about 55%, about 35% to about 50%, or about 40% to about45%.

A percent void space (which can also be referred to as a “percentporosity”) can be measured by image analysis of a cross-section of alayer or by measuring the bulk density of sample of a layer using apycnometer. Unless specified otherwise, a percent void space reportedherein is measured by image analysis of a cross-section of a layer. Theimages are analyzed using ImageJ software (or equivalent software) at37× magnification. The ImageJ software uses a trainable Wekasegmentation classifier to calculate the percent void space in thelayer. For purposes of calculating a percent void space, three to fiveseparate images of a cross-section are evaluated, and the averagepercent void space is reported as the percent void space for the layer.In some embodiments, protein polyurethane alloy layer 1720 can includeone or more foaming agents and/or foam stabilizers. Suitable foamingagents and foam stabilizers include those discussed herein for layers1730 and 1740.

Substrate layer 1710 includes a bottom surface 1712, a top surface 1714,and a thickness 1716 measured between bottom surface 1712 and topsurface 1714. In some embodiments, thickness 1716 can range from about50 microns to about 1000 microns, including subranges. For example,thickness 1716 can be about 50 microns, about 100 microns, about 150microns, about 200 microns, about 250 microns, about 300 microns, about350 microns, about 400 microns, about 500 microns, about 600 microns,about 700 microns, about 800 microns, about 900 microns, or about 1000microns, or within a range having any two of these values as endpoints,inclusive of the endpoints. In some embodiments, thickness 1716 canrange from about 100 microns to about 900 microns, about 150 microns toabout 800 microns, about 200 microns to about 700 microns, about 250microns to about 600 microns, about 300 microns to about 500 microns, orabout 350 microns to about 400 microns.

Substrate layer 1710 can have a dry weight, measured in grams per squaremeter (g/m²), ranging from about 50 g/m² to about 600 g/m², includingsubranges. For example, substrate layer 110 can have a dry weight ofabout 50 g/m², about 75 g/m², about 100 g/m², about 125 g/m², about 150g/m², about 175 g/m², about 200 g/m², about 300 g/m², about 400 g/m²,about 500 g/m², or about 600 g/m², or within a range having any two ofthese values as endpoints. In some embodiments, substrate layer 1710 canhave a dry weight ranging from about 75 g/m² to about 500 g/m², about100 g/m² to about 400 g/m², about 125 g/m² to about 300 g/m², about 150g/m² to about 200 g/m², or about 175 g/m² to about 200 g/m².

Substrate layer 1710 can include one or more textile layers. The one ormore textile layers can be, for example, a woven layer, a non-wovenlayer, a knit layer, a mesh fabric layer, or a leather layer. The one ormore textile layer can be comprised of recycled or virgin fibers,filaments or yarns. In some embodiments, substrate layer 1710 can be, orcan include, a polyester knit layer, a polyester cotton spandex blendknit layer, or a suede layer. In some embodiments, substrate layer 1710can be made from one or more natural fibers, for example fibers madefrom cotton, linen, silk, wool, kenaf, flax, cashmere, angora, bamboo,bast, hemp, soya, seacell, milk or milk proteins, spider silk, chitosan,mycelium, cellulose including bacterial cellulose, or wood. Mycelium isthe vegetative part of a fungus or fungus-like bacterial colony,composed of a mass of branching, thread-like hyphae. Fungi are composedprimarily of a cell wall that is constantly being extended at the apexof the hyphae. Unlike the cell wall of a plant, which is composedprimarily of cellulose, or the structural component of an animal cell,which relies on collagen, the structural oligosaccharides of the cellwall of fungi rely primarily on chitin and beta glucan. Chitin is astrong, hard substance, also found in the exoskeletons of arthropods.

In some embodiments, substrate layer 1710 can be made from one or moresynthetic fibers, for example fibers made from polyesters, nylons,aromatic polyamides, polyolefin fibers such as polyethylene,polypropylene, rayon, lyocell, viscose, antimicrobial yarn (A.M.Y.),Sorbtek, nylon, elastomers such as LYCRA®, spandex, or ELASTANE®,polyester-polyurethane copolymers, aramids, carbon including carbonfibers and fullerenes, glass, silicon, minerals, metals or metal alloysincluding those containing iron, steel, lead, gold, silver, platinum,copper, zinc, and titanium, or mixtures thereof.

In some embodiments, non-woven substrate layer 1710 can be a staplenon-woven, melt-blown non-woven, spunlaid non-woven, flashspunnon-woven, or a combination thereof. In some embodiments, non-wovensubstrate layer 1710 can be made by carding, can be air-laid, or can bewet-laid. In some embodiments, the carded, air-laid, or wet-laidsubstrates can be bonded by, for example, needle-punch,hydroentanglement, lamination, or thermal bonding. In some embodiments,non-woven substrate layer 1710 can include one or more natural fibers,for example fibers made from cotton, linen, silk, wool, kenaf, flax,cashmere, angora, bamboo, bast, hemp, soya, seacell, milk or milkproteins, spider silk, chitosan, mycelium, cellulose including bacterialcellulose, or wood.

In some embodiments, non-woven substrate layer 1710 can includepolymeric fibers with functional particles in the polymer. Exemplaryfunctional particles include ceramic particles mixed in a polymericresin during an extrusion process for making the polymeric fibers. Suchceramic particles can provide the polymeric fibers with desirable heatdissipation and flame resistance properties. In some embodiments,non-woven substrate layer 1710 can include fibers made of fruit pulp(e.g., grape pulp or apple pulp) or pineapple fibers. In someembodiments, non-woven substrate layer 1710 can include fibers made fromrecycled materials, for example recycled plastics. In some embodiments,non-woven substrate layer 1710 can include algae fibers. In someembodiments, a non-woven substrate layer 1710 can include cork fibers.

In some embodiments, substrate layer 1710 can be, or can include, aspacer fabric, for example spacer fabric 2100, shown in FIG. 21. Spacerfabric 2100 includes a first fabric layer 2110 and a second fabric layer2120 connected by one or more spacer yarns 2130. Spacer yarn(s) 2130 aredisposed between first fabric layer 2110 and second fabric layer 2120and define a distance between an interior surface 2114 of first fabriclayer 2110 and an interior surface 2124 of second fabric layer 2120.Exterior surface 2112 of first fabric layer 2110 and exterior surface2122 of second fabric layer 2120 can define top surface 1714 and bottomsurface 1712 of substrate layer 1710, respectively.

First fabric layer 2110 and second fabric layer 2120 can include one ormore layers of fabric material. In some embodiments, first fabric layer2110 and second fabric layer 2120 can include one or more textile layersmade from staple fibers, filaments, or mixtures thereof. As used herein,“staple fibers” are fibers having a short length, between about 0.2 mmto about 5 centimeters (cm). Staple fibers can be naturally occurring orcan be cut filaments. As used herein, “filaments” are long fibers havinga length of 5 cm or more. In some embodiments, first fabric layer 2110and second fabric layer 2120 can include one or more layers of a wovenmaterial or a knitted material. In some embodiments, exterior surface2112 of first fabric layer 2110 can be defined by a woven fabric layeror a knitted fabric layer. In some embodiments, exterior surface 2122 ofsecond fabric layer 2120 can be defined by a woven fabric layer or aknitted fabric layer.

In some embodiments, first fabric layer 2110 and second fabric layer2120 can be made from one or more natural fibers, for example fibersmade from cotton, linen, silk, wool, kenaf, flax, cashmere, angora,bamboo, bast, hemp, soya, seacell, milk or milk proteins, spider silk,chitosan, mycelium, cellulose including bacterial cellulose, or wood. Insome embodiments, first fabric layer 2110 and second fabric layer 2120can be made from one or more synthetic fibers, for example fibers madefrom polyesters, nylons, aromatic polyamides, polyolefin fibers such aspolyethylene, polypropylene, rayon, lyocell, viscose, antimicrobial yarn(A.M.Y.), Sorbtek, nylon, elastomers such as LYCRA®, spandex, orELASTANE®, polyester-polyurethane copolymers, aramids, carbon includingcarbon fibers and fullerenes, glass, silicon, minerals, metals or metalalloys including those containing iron, steel, lead, gold, silver,platinum, copper, zinc, and titanium, or mixtures thereof. Spaceryarn(s) 2130 can include mono-filament yarn(s) composed of any of thenatural or synthetic materials listed above for first fabric layer 2110and second fabric layer 2120.

In some embodiments, substrate layer 1710 can be colored with a coloringagent. In some embodiments the coloring agent can be a dye, for examplean acid dye, a fiber reactive dye, a direct dye, a sulfur dye, a basicdye, or a reactive dye. In some embodiments, the coloring agent can bepigment, for example a lake pigment. In some embodiments, a firstcoloring agent can be incorporated into one or more protein polyurethanealloy layers and a second coloring agent can be incorporated intosubstrate layer 1710, depending on the desired aesthetic of a layeredmaterial.

A fiber reactive dye includes one or more chromophores that containpendant groups capable of forming covalent bonds with nucleophilic sitesin fibrous, cellulosic substrates in the presence of an alkaline pH andraised temperature. These dyes can achieve high wash fastness and a widerange of brilliant shades. Exemplary fiber reactive dyes, include butare not limited to, sulphatoethylsulphone (Remazol), triazine,vinylsulphone, and acrylamido dyes. These dyes can dye protein fiberssuch as silk, wool and nylon by reacting with fiber nucleophiles via aMichael addition. Direct dyes are anionic dyes capable of dyingcellulosic or protein fibers. In the presence of an electrolyte such assodium chloride or sodium sulfate, near boiling point, these dyes canhave an affinity to cellulose. Exemplary direct dyes include, but arenot limited to, azo, stilbene, phthalocyanine, and dioxazine.

In some embodiments, layered material 1700 can include a proteinpolyurethane alloy layer 1720 attached to top surface 1714 of substratelayer 1710. In some embodiments, bottom surface 1722 of proteinpolyurethane alloy layer 1720 can be in direct contact with top surface1714 of substrate layer 1710. In some embodiments, bottom surface 1722of protein polyurethane alloy layer 1720 can be attached to top surface1714 of substrate layer 1710 via an adhesive layer (e.g., adhesive layer1750). In some embodiments, layered material 1700 can include a proteinpolyurethane alloy layer 1720 attached to bottom surface 1712 ofsubstrate layer 1710. In some embodiments, top surface 1724 of proteinpolyurethane alloy layer 1720 can be in direct contact with bottomsurface 1712 of substrate layer 1710. In some embodiments, top surface1724 of protein polyurethane alloy layer 1720 can be attached to bottomsurface 1712 of substrate layer 1710 via an adhesive layer (e.g.,adhesive layer 1750). In some embodiments, layered material 1700 caninclude a protein polyurethane alloy layer 1720 attached to top surface1714 of substrate layer 1710 and a protein polyurethane alloy layer 1720attached to bottom surface 1712 of substrate layer 1710. In suchembodiments, layered material 1700 includes protein polyurethane alloylayers 1720 disposed on opposing surfaces of substrate layer 1710.

In some embodiments, as shown for example in FIG. 18, layered material1700 can include a second protein polyurethane alloy layer 1730 disposedbetween protein polyurethane alloy layer 1720 and substrate layer 1710.In such embodiments, second protein polyurethane alloy layer 1730 isattached to protein polyurethane alloy layer 1720. In some embodiments,bottom surface 1722 of protein polyurethane alloy layer 1720 can be indirect contact with a top surface 1734 of second protein polyurethanealloy layer 1730.

Second protein polyurethane alloy layer 1730 includes a bottom surface1732, top surface 1734, and a thickness 1736 measured between bottomsurface 1732 and top surface 1734. In some embodiments, thickness 1736can range from about 25 microns to about 600 microns, includingsubranges. For example, thickness 1736 can be about 25 microns, about 50microns, about 100 microns, about 125 microns, about 150 microns, about175 microns, about 200 microns, about 225 microns, about 250 microns,about 275 microns, about 300 microns, about 400 microns, about 500microns, or about 600 microns, or within a range having any two of thesevalues as endpoints, inclusive of the endpoints. In some embodiments,thickness 1736 can range from about 50 microns to about 500 microns,about 75 microns to about 400 microns, about 100 microns to about 300microns, about 125 microns to about 275 microns, about 150 microns toabout 250 microns, about 175 microns to about 225 microns, or about 200microns to about 225 microns. In some embodiments, thickness 1736 can begreater than thickness 1726. In some embodiments, thickness 1736 can beless than thickness 1726. In some embodiments, thickness 1736 can begreater than or less than thickness 1726 by 5 microns or more.

Second protein polyurethane alloy layer 1730 can have a dry weight,measured in grams per square meter (g/m²), ranging from about 30 g/m² toabout 600 g/m², including subranges. For example, second proteinpolyurethane alloy layer 1730 can have a dry weight of about 30 g/m²,about 40 g/m², about 60 g/m², about 80 g/m², about 100 g/m², about 120g/m², about 140 g/m², about 150 g/m², about 200 g/m², about 300 g/m²,about 400 g/m², about 500 g/m², or about 600 g/m², or within a rangehaving any two of these values as endpoints, inclusive of the endpoints.In some embodiments, second protein polyurethane alloy layer 1730 canhave a dry weight ranging from about 40 g/m² to about 500 g/m², about 60g/m² to about 400 g/m², about 80 g/m² to about 300 g/m², about 100 g/m²to about 200 g/m², about 120 g/m² to about 150 g/m², or about 140 g/m²to about 150 g/m². In some embodiments, protein polyurethane alloy layer1720 can have a first weight and second protein polyurethane alloy layer1730 can have a second weight, and the first weight can be less than thesecond weight. In some embodiments, the first weight can be less thanthe second weight by 5 g/m² or more.

In some embodiments, second protein polyurethane alloy layer 1730 caninclude a foaming agent. In some embodiments, second proteinpolyurethane alloy layer 1730 can include a foam stabilizer. The foamingagent or foam stabilizer can facilitate the formation of voids in secondprotein polyurethane alloy layer 1730 during blending of second proteinpolyurethane alloy layer 1730. Suitable foam stabilizers include, butare not limited to, HeiQ Chemtex 2216-T (a stabilized blend of nonionicand anionic surfactants), HeiQ Chemtex 2241-A (a modified HEUR(hydrophobically-modified ethylene oxide urethane) thickener), HeiQChemtex 2243 (a non-ionic silicone dispersion), or HeiQ Chemtex 2317 (astabilized blend of nonionic and anionic surfactants) foam stabilizersavailable from HeiQ Chemtex. When used, a foam stabilizer serves tostabilize mechanically created foam (air voids). The mechanicallycreated foam may be created by, for example, a rotor and/or compressedair. When used, a foaming agent can create foam (air voids) within alayer by a chemical reaction and/or via heat generation within thelayer.

In some embodiments, second protein polyurethane alloy layer 1730 can bereferred to as a “foamed protein polyurethane alloy layer” becauseeither (i) layer 1730 includes one or more foaming agents or foamstabilizers and/or (ii) layer 1730 includes a density less than proteinpolyurethane alloy layer 1720.

Second protein polyurethane alloy layer 1730 can have a density,measured in the percent void space for layer 1730, ranging from about 5%void space to about 70% void space, including subranges. For example,second protein polyurethane alloy layer 1730 can have about 5% voidspace, about 10% void space, about 20% void space, about 30% void space,about 35% void space, about 40% void space, about 45% void space, about50% void space, about 55% void space, about 60% void space, about 65%void space, or about 70% void space, or within a range having any two ofthese values as endpoints, inclusive of the endpoints. In someembodiments, second protein polyurethane alloy layer 1730 can have apercent void space ranging from about 10% to about 65%, about 20% toabout 60%, about 30% to about 55%, about 35%, to about 50%, or about 40%to about 45%. In some embodiments, protein polyurethane alloy layer 1720can have a first density and second protein polyurethane alloy layer1730 can have a second density, and the first density can be greaterthan the second density. In some embodiments, the first density can begreater than the second density by 5% void space or more.

Layering a plurality of protein polyurethane alloy layers havingdifferent weights and/or densities can be used to tailor the materialproperties of a layered material. For example, layers having lighterweights and/or densities can be used to increase the softness and/orflexibility of a layered material. On the other hand, layers having highweights and/or densities can increase the strength of the layeredmaterial. Additionally, using one or more layers having relativelylighter weight and/or density can increase the ease in which cutting,stitching, and/or shaping process steps (e.g., skyving) can be performedon a layered material. Layering a plurality of protein polyurethanealloy layers gives lot of freedom in designing of a material.

In some embodiments, second protein polyurethane alloy layer 1730 canfurther include, in addition to any other components that may bepresent, such as a foaming agent, a foam stabilizer, or one or morecoloring agents. The coloring agent type and content for second proteinpolyurethane alloy layer 1730 can be any of the types and amountsdescribed herein for protein polyurethane alloy layer 1720. In someembodiments, second protein polyurethane alloy layer 1730 can be free orsubstantially free of a coloring agent.

In some embodiments, as shown for example in FIG. 18, layered material1700 can include a third protein polyurethane alloy layer 1740 disposedbetween second protein polyurethane alloy layer 1730 and substrate layer1710. In such embodiments, third protein polyurethane alloy layer 1740is attached to second protein polyurethane alloy layer 1730. In someembodiments, bottom surface 1732 of second protein polyurethane alloylayer 1730 can be in direct contact with a top surface 1744 of thirdprotein polyurethane alloy layer 1740.

Third protein polyurethane alloy layer 1740 includes a bottom surface1742, top surface 1744, and a thickness 1746 measured between bottomsurface 1742 and top surface 1744. In some embodiments, thickness 1746can range from about 25 microns to about 600 microns, includingsubranges. For example, thickness 1746 can be about 25 microns, about 50microns, about 100 microns, about 125 microns, about 150 microns, about175 microns, about 200 microns, about 225 microns, about 250 microns,about 275 microns, about 300 microns, about 400 microns, about 500microns, or about 600 microns, or within a range having any two of thesevalues as endpoints, inclusive of the endpoints. In some embodiments,thickness 1746 can range from about 50 microns to about 500 microns,about 75 microns to about 400 microns, about 100 microns to about 300microns, about 125 microns to about 275 microns, about 150 microns toabout 250 microns, about 175 microns to about 225 microns, or about 175microns to about 200 microns. In some embodiments, thickness 1746 can begreater than thickness 1726. In some embodiments, thickness 1746 can beless than thickness 1726. In some embodiments, thickness 1746 can begreater than or less than thickness 1726 by 5 microns or more. In someembodiments, thickness 1746 can be the same as thickness 1736. In someembodiments, thickness 1746 can be greater than or less than thickness1736. In some embodiments, thickness 1746 can be greater than or lessthan thickness 1736 by 5 microns or more.

Third protein polyurethane alloy layer 1740 can have a dry weight,measured in grams per square meter (g/m²), ranging from about 30 g/m² toabout 600 g/m², including subranges. For example, third proteinpolyurethane alloy layer 1740 can have a dry weight of about 30 g/m²,about 40 g/m², about 60 g/m², about 80 g/m², about 100 g/m², about 120g/m², about 140 g/m², about 150 g/m², about 200 g/m², about 300 g/m²,about 400 g/m², about 500 g/m², or about 600 g/m², or within a rangehaving any two of these values as endpoints, inclusive of the endpoints.In some embodiments, third protein polyurethane alloy layer 1740 canhave a dry weight ranging from about 40 g/m² to about 500 g/m², about 60g/m² to about 400 g/m², about 80 g/m² to about 300 g/m², about 100 g/m²to about 200 g/m², about 120 g/m² to about 150 g/m², or about 120 g/m²to about 140 g/m². In some embodiments, protein polyurethane alloy layer1720 can have a first weight and third protein polyurethane alloy layer1740 can have a third weight, and the first weight can be less than thethird weight. In some embodiments, protein polyurethane alloy layer 1720can have a first weight, second protein polyurethane alloy layer 1730can have a second weight, and third protein polyurethane alloy layer1740 can have a third weight, and the first weight can be less than thesecond weight and the third weight. In some embodiments, the firstweight can be less than the second weight and/or the third weight by 5g/m² or more.

In some embodiments, third protein polyurethane alloy layer 1740 caninclude a foaming agent. In some embodiments, third protein polyurethanealloy layer 1740 can include a foam stabilizer. The foaming agent and/orfoam stabilizer can facilitate the formation of voids in third proteinpolyurethane alloy layer 1740 during blending of third proteinpolyurethane alloy layer 1740. Suitable foaming agents include, but arenot limited to, HeiQ Chemtex 2216-T (a stabilized blend of nonionic andanionic surfactants), HeiQ Chemtex 2241-A (a modified HEUR(hydrophobically-modified ethylene oxide urethane) thickener), HeiQChemtex 2243 (a non-ionic silicone dispersion), or HeiQ Chemtex 2317 (astabilized blend of nonionic and anionic surfactants) foam stabilizersavailable from HeiQ Chemtex.

In some embodiments, third protein polyurethane alloy layer 1740 can bereferred to as a “foamed protein polyurethane alloy layer” becauseeither (i) layer 1740 includes one or more foaming agents or foamstabilizers and/or (ii) layer 1740 includes a density less than proteinpolyurethane alloy layer 120.

Third protein polyurethane alloy layer 1740 can have a density, measuredin the percent void space for layer 1740, ranging from about 5% voidspace to about 70% void space, including subranges. For example, thirdprotein polyurethane alloy layer 1740 can have about 5% void space,about 10% void space, about 20% void space, about 30% void space, about35% void space, about 40% void space, about 45% void space, about 50%void space, about 55% void space, about 60% void space, about 65% voidspace, or about 70% void space, or within a range having any two ofthese values as endpoints, inclusive of the endpoints. In someembodiments, third protein polyurethane alloy layer 1740 can have apercent void space ranging from about 10% to about 65%, about 20% toabout 60%, about 30% to about 55%, about 35% to about 50%, or about 40%to about 45%. In some embodiments, protein polyurethane alloy layer 1720can have a first density and third protein polyurethane alloy layer 1740can have a third density, and the first density can be greater than thethird density. In some embodiments, protein polyurethane alloy layer1720 can have a first density, second protein polyurethane alloy layer1730 can have a second density, and third protein polyurethane alloylayer 1740 can have a third density, and the first density can begreater than the second density and third density. In some embodiments,the first density can be greater than the second density and/or thethird density by 5% void space or more.

In some embodiments, layered material 1700 can include a plurality ofprotein polyurethane alloy layers having the same protein andpolyurethane. In some embodiments, layered material 1700 can include aplurality of protein polyurethane alloy layers and the different layerscan have a different protein and/or a different polyurethane.

In some embodiments, third protein polyurethane alloy layer 1740 canfurther include, in addition to any other components that may bepresent, such as a foaming agent, a foam stabilizer, one or morecoloring agents. The coloring agent type and content for third proteinpolyurethane alloy layer 1740 can be any of the types and amountsdescribed herein for protein polyurethane alloy layer 1720. In someembodiments, third protein polyurethane alloy layer 1740 can be free orsubstantially free of a coloring agent.

In some embodiments, and as shown for example in FIG. 18, layeredmaterial 1700 can include a basecoat layer 1760. Basecoat layer 1760 canbe disposed over top surface 1724 of protein polyurethane alloy layer1720. Basecoat layer 1760 can be directly or indirectly attached toprotein polyurethane alloy layer 1720. In some embodiments, basecoatlayer 1760 can be disposed on top surface 1724 of protein polyurethanealloy layer 1720. In some embodiments, a bottom surface 1762 of basecoatlayer 1760 can be in direct contact with top surface 1724 of proteinpolyurethane alloy layer 1720.

Basecoat layer 1760 includes bottom surface 1762, a top surface 1764,and a thickness 1766 measured between bottom surface 1762 and topsurface 1764. In some embodiments, thickness 1766 can range from about20 microns to about 200 microns, including subranges. For example,thickness 1766 can be about 20 microns, about 30 microns, about 40microns, about 50 microns, about 60 microns, about 70 microns, about 80microns, about 90 microns, about 100 microns, about 150 microns, orabout 200 microns, or within a range having any two of these values asendpoints, inclusive of the endpoints. In some embodiments, thickness1766 can range from about 30 microns to about 150 microns, about 40microns to about 100 microns, about 50 microns to about 90 microns,about 60 microns to about 80 microns, or about 60 microns to about 70microns.

In embodiments including basecoat layer 1760, basecoat layer 1760 canprovide one or more of the following properties for layered material1700: (i) abrasion performance, color fastness, or hydrolyticresistance. Basecoat layer 1760 may also serve to adhere to a top-coatlayer to layered material 1700 in embodiments including a top-coatlayer. In some embodiments, basecoat layer 1760 can include one or morepolymeric materials. Suitable materials for basecoat layer 1760 include,but are not limited to, polyether polyurethanes, polycarbonatepolyurethanes, polyester polyurethanes, acrylic polymers, andcross-linkers such as isocyanate or carbodiimide. In some embodiments,layered material 1700 can include a plurality of basecoat layers 1760.In some embodiments, basecoat layer 1760 can be absent from layeredmaterial 1700.

Basecoat layer 1760 can have a dry weight, measured in grams per squaremeter (g/m²), ranging from about 20 g/m² to about 100 g/m², includingsubranges. For example, basecoat layer 1760 can have a dry weight ofabout 20 g/m², about 30 g/m², about 40 g/m², about 50 g/m², about 60g/m², about 70 g/m², about 80 g/m², about 90 g/m², or about 100 g/m², orwithin a range having any two of these values as endpoints, inclusive ofthe endpoints. In some embodiments, basecoat layer 1760 can have a dryweight ranging from about 30 g/m² to about 90 g/m², about 40 g/m² toabout 80 g/m², or about 50 g/m² to about 70 g/m².

In some embodiments, as shown for example in FIG. 18, layered material1700 can include a top-coat layer 1770. Top-coat layer 1770 can bedisposed over top surface 1724 of protein polyurethane alloy layer 1720.Top-coat layer 1770 can be directly or indirectly attached to proteinpolyurethane alloy layer 1720. In some embodiments, a bottom surface1772 of top-coat layer 1770 can be in direct contact with top surface1724 of protein polyurethane alloy layer 1720. In embodiments includingbasecoat layer 1760, top-coat layer 1770 can be disposed over topsurface 1764 of basecoat layer 1760. In some embodiments, top-coat layer1770 can be disposed on top surface 1764 of basecoat layer 1760. In someembodiments, a bottom surface 1772 of top-coat layer 1770 can be indirect contact with top surface 1764 of basecoat layer 1760.

Top-coat layer 1770 includes bottom surface 1772, a top surface 1774,and a thickness 1776 measured between bottom surface 1772 and topsurface 1774. In some embodiments, thickness 1776 can range from about10 microns to about 80 microns, including subranges. For example,thickness 1776 can be about 10 microns, about 20 microns, about 30microns, about 40 microns, about 50 microns, about 60 microns, about 70microns, or about 80 microns, or within a range having any two of thesevalues as endpoints, inclusive of the endpoints. In some embodiments,thickness 1776 can range from about 20 microns to about 70 microns,about 30 microns to about 60 microns, or about 30 microns to about 50microns.

In embodiments including top-coat layer 1770, top-coat layer 1770 canprovide one or more of the following properties for layered material1700: surface feel, stain resistance, flame resistance, gloss level, orcolor appearance. In some embodiments, top-coat layer 1770 can includeone or more polymeric materials. Suitable materials for top-coat layer1770 include but are not limited to, polyurethanes, acrylics,silicone-based feel agents, matte agents, and gloss agents. In someembodiments, layered material 1700 can include a plurality of top-coatlayers 1770. In some embodiments, top-coat layer 1770 can be absent fromlayered material 1700. In some embodiments, top-coat layer 1770 can betransparent or translucent. In some embodiments, top-coat layer 1770 caninclude one or more dyes, one or more pigments and/or one or morereflective agents to affect appearance.

Top-coat layer 1770 can have a dry weight, measured in grams per squaremeter (g/m²), ranging from about 10 g/m² to about 80 g/m², includingsubranges. For example, top-coat layer 1770 can have a dry weight ofabout 10 g/m², about 20 g/m², about 30 g/m², about 40 g/m², about 50g/m², about 60 g/m², about 70 g/m², or about 80 g/m², or within a rangehaving any two of these values as endpoints, inclusive of the endpoints.In some embodiments, top-coat layer 1770 can have a dry weight rangingfrom about 20 g/m² to about 70 g/m², about 30 g/m² to about 60 g/m², orabout 30 g/m² to about 50 g/m².

Together, protein polyurethane alloy layer(s) 1720, 1730, 1740, basecoatlayer(s) 1760, and/or top-coat layer(s) 1770 can define a layeredassembly 1780 of a layered material 1700. Layered assembly 1780 caninclude any number of protein polyurethane alloy layers as describedherein. For example, layered assembly 1780 can include 2, 3, 4, 5, 6, 7,8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 protein polyurethanealloy layers. In some embodiments, layered material 1700 can include alayered assembly 1780 attached to bottom surface 1712 of substrate layer1710. Layered assembly 1780 attached to bottom surface 1712 of substratelayer 1710 can include any of the layers and materials as describedherein for a layered assembly 1780 attached to top surface 1714 ofsubstrate layer 1710. In some embodiments, layered material 1700 caninclude a layered assembly 1780 attached to top surface 1714 ofsubstrate layer 1710 and a layered assembly 1780 attached to bottomsurface 1712 of substrate layer 1710. In such embodiments, layeredmaterial 1700 includes layered assemblies 1780 disposed over opposingsurfaces 1712 and 1714 of substrate layer 1710.

In some embodiments, a protein polyurethane alloy layer of layeredmaterial 1700 is attached to a surface of substrate layer 1710 with anadhesive layer 1750. In such embodiments, adhesive layer 1750 includes abottom surface 1752, a top surface 1754, and a thickness 1756 measuredbetween bottom surface 1752 and top surface 1754. In some embodiments,thickness 1756 can range from about 10 microns to about 50 microns,including subranges. For example, thickness 1756 can be about 10microns, about 20 microns, about 30 microns, about 40 microns, or about50 microns, or within a range having any two of these values asendpoints, inclusive of the endpoints. In some embodiments, thickness1756 can range from about 20 microns to about 40 microns. Suitableadhesives for adhesive layer 1750 include, but are not limited to,polyurethane adhesives, hot melt adhesives, emulsion polymer adhesives,dry web adhesives, dry laminating adhesives, or wet laminatingadhesives. Hauthane HD-2001 available from C.L. Hauthaway & SonsCorporation is an exemplary laminating adhesive suitable for adhesivelayer 1750. Exemplary polyurethane adhesives include, but are notlimited to, L-2183, L-2245, L-2255 from Hauthaway and IMPRANIL® DAH, DAAfrom Covestro. Exemplary dry web adhesives include, but are not limitedto, 9D8D20 from Protechnic. In some embodiments, layered material 1700does not include an adhesive layer 1750.

Adhesive layer 1750 can have a dry weight, measured in grams per squaremeter (g/m²), ranging from about 10 g/m² to about 50 g/m², includingsubranges. For example, adhesive layer 1750 can have a dry weight ofabout 10 g/m², about 20 g/m², about 30 g/m², about 40 g/m², or about 50g/m², or within a range having any two of these values as endpoints,inclusive of the endpoints. In some embodiments, adhesive layer 1750 canhave a dry weight ranging from about 20 g/m² to about 40 g/m².

Layered material 1700 can be made by attaching one or more proteinpolyurethane alloy layers, and one or more basecoat and/or top-coatlayers described herein, to substrate layer 1710. In some embodiments,the layer(s) may be subsequently layered over a surface of a substratelayer. Layer(s) can be attached to either top surface 1714 and/or bottomsurface 1712 of substrate layer 1710. In some embodiments, the layer(s)can be layered over a sacrificial layer that is removed after layeringand before or after attaching the one or more layers to substrate layer1710. Each protein polyurethane alloy layer of a layered material can bedeposited using any suitable coating technique, including, but notlimited to, knife over roll coating, gravure coating, slot die coating,multi-layer slot die coating, or curtain coating. Multi-layer slot diecoating can allow simultaneous coating of multiple adjacent layers.

In some embodiments, a substrate layer 1710 can be coated with anadhesive layer 1750 and additional layers (e.g., layers 1720, 1730,1740, 1760, and/or 1770) can be formed over adhesive layer 1750 in anyappropriate order. In such embodiments, the layers can be formed overadhesive layer 1750 in the same manner as described below for method1900 with the layers being formed over the adhesive layer 1750 ratherthan a sacrificial layer. In some embodiments, a blended mixture asdescribed herein can be applied directly to a surface of a substratelayer 1710, using for example, a coating or pouring process. In suchembodiments, the blended mixture can penetrate at least a portion ofsubstrate layer 1710. After application, the blended mixture can bedried to form a protein polyurethane alloy layer (e.g., layer 1720). Insome embodiments, after drying, the protein polyurethane alloy layer andthe substrate layer 1710 can be heated (e.g., heat pressed) to aid inattaching the layers together. Before or after drying and/or before orafter attaching the protein polyurethane alloy layer and substrate layer1710, other layers (e.g., layers 1730, 1740, 1760, and/or 1770) can beapplied over the protein polyurethane alloy layer in any appropriateorder. In such embodiments, the other layers can be formed over theprotein polyurethane alloy layer in the same manner as described belowfor method 1900 with the layers being formed over the proteinpolyurethane alloy layer rather than a sacrificial layer.

In some embodiments, decorative layers can be applied between layers ofa layered material during manufacturing. For example, a logo, anartistic pattern, a drawing, or a symbol can be applied to a first layerbefore disposing another layer over the first layer. Decorative layerscan be applied using, for example, screen printing, digital printing, ortransfer printing.

In some embodiments, the layers of a layered material can be formed overa sacrificial layer and attached to a substrate layer after formation.FIG. 19 illustrates a method 1900 for making a layered material 1700according to some embodiments. FIGS. 20A-20F illustrate steps of method1900. Unless stated otherwise, the steps of method 1900 need not beperformed in the order set forth herein. Additionally, unless specifiedotherwise, the steps of method 1900 need not be performed sequentially.The steps can be performed simultaneously. As one example, method 1900need not include a solvent removal step after the deposition of eachindividual protein polyurethane alloy layer; rather the solvent (forexample, water) from a plurality of protein polyurethane alloy layerscan be removed in a single step. Method 1900 can be used to attachlayers to one or both sides of a substrate layer 1710.

In step 1902, a top-coat layer 1770 can be disposed over a top surface2002 of a sacrificial layer 2000, as illustrated in for example FIG.20A. Top-coat layer 1770 can be disposed over sacrificial layer 2000using any suitable coating technique, for example, knife over roll withreverse transfer paper, spraying, or roller coating. Sacrificial layer2000 is a layer of material that does not define a layer of layeredmaterial 1700. Rather, sacrificial layer 2000 is removed duringmanufacturing of layered material 1700. Sacrificial layer 2000 can beremoved mechanically, such as by peeling away, or chemically, forexample, by dissolving sacrificial layer 2000. In some embodiments,sacrificial layer 2000 can be a release liner. Suitable materials forsacrificial layer 2000 include but are not limited to grain texturerelease papers. Exemplary grain texture release papers include, releasepapers available from Sappi paper, for example, Matte Freeport 189,Freeport 123, or Expresso 904. In some embodiments, method 1900 does notinclude step 1902. That is, step 1902 is optional. In some embodiments,top-coat layer 1770 can be applied to a layered material 1700 afterremoving sacrificial layer 2000 in step 1918. In some embodiments,top-coat layer 1770 can be applied to a layered material 1700 afterattaching protein polyurethane alloy layer(s) to a substrate layer 1710in step 1920.

In step 1904, basecoat layer 1760 can be disposed over sacrificial layer2000, as illustrated in for example FIG. 20B. In embodiments includingtop-coat layer 1770, basecoat layer 1760 can be disposed over top-coatlayer 1770. Basecoat layer 1760 can disposed over sacrificial layer 2000using any suitable coating technique, for example, knife over roll withreverse transfer paper, spraying, or roller coating. In someembodiments, method 1900 does not include step 1904. Step 1904 isoptional. In some embodiments, basecoat layer 1760 can be applied to alayered material 1700 after removing sacrificial layer 2000 in step1918. In some embodiments, basecoat layer 1760 can be applied to alayered material 1700 after attaching protein polyurethane alloylayer(s) to a substrate layer 1710 in step 1920.

In step 1906, one or more polyurethanes dispersed or dissolved in anaqueous solution can be blended with one or more proteins to form ablended mixture in the aqueous solution. In some embodiments, the one ormore polyurethanes can be dispersed or dissolved in an aqueous solutionbefore blending with protein(s). In some embodiments, the one or morepolyurethanes can become dispersed or dissolved in an aqueous solutionduring blending with protein(s). In some embodiments, the one or morepolyurethanes and the one or more proteins can be blended in a suitablevessel until a homogenous blend is formed. Suitable blending equipmentincludes, but is not limited to, a blender, a stand mixer, an in-linemixer, or a high shear mixer.

In some embodiments, protein(s) can be dispersed or dissolved in anaqueous solution before blending with polyurethane in step 1906.Suitable aqueous solutions include, but are not limited to, water, anaqueous alkali solution, an aqueous acid solution, an aqueous solutionincluding an organic solvent, a urea solution, and mixtures thereof. Insome embodiments, the aqueous alkali solution can be a basic solutionsuch as a sodium hydroxide, ammonia or ammonium hydroxide solution. Insome embodiments, examples of an acidic aqueous solution can be anacetic acid or hydrochloric acid (HCl) solutions. Suitable organicsolvents include, but are not limited to, ethanol, isopropanol, acetone,ethyl acetate, isopropyl acetate, glycerol, and the like. In someembodiments, the protein concentration in the aqueous protein mixturecan range from about 10 g/L to about 300 g/L, including subranges. Forexample, the protein concentration in the aqueous protein mixture can beabout 10 g/L, about 20 g/L, about 30 g/L, about 40 g/L, about 50 g/L,about 60 g/L, about 70 g/L, about 80 g/L, about 90 g/L, about 100 g/L,about 150 g/L, about 200 g/L, about 250 g/L, or about 300 g/L, or withina range having any two of these values as endpoints, inclusive of theendpoints. In some embodiments, the protein concentration in the aqueousprotein mixture can range from about 10 g/L to about 300 g/L, about 20g/L to about 250 g/L, about 30 g/L to about 200 g/L, about 40 g/L toabout 150 g/L, about 50 g/L to about 100 g/L, about 60 g/L to about 90g/L, or about 70 g/L to about 80 g/L.

The amount of protein in a protein/polyurethane blend can range fromabout 5 wt % to about 60%, based on the weight of protein andpolyurethane, including subranges. For example, the amount of protein ina blend can be about 5 wt %, about 10 wt %, about 15 wt %, about 20 wt%, about 25 wt %, about 30 wt %, about 35 wt %, about 40 wt %, about 45wt %, about 50 wt %, about 55 wt %, or about 60 wt %, or within a rangehaving any two of these values as endpoints. In some embodiments, theamount of protein in a blend can be about 10 wt % to about 55 wt %,about 15 wt % to about 50 wt %, about 20 wt % to about 45 wt %, about 25wt % to about 40 wt %, or about 30 wt % to about 35 wt %. In someembodiments, the amount of protein in the protein/polyurethane blend canrange from 20 wt % to 40 wt %.

The amount of polyurethane(s) in a protein/polyurethane blend can rangefrom about 10 wt % to about 85 wt %, based on the weight of protein andpolyurethane, including subranges. For example, the amount ofpolyurethane(s) in blend can be about 10 wt %, about 15 wt %, about 20wt %, about 25 wt %, about 30 wt %, about 35 wt %, about 40 wt %, about45 wt %, about 50 wt %, about 55 wt %, about 60 wt %, about 65 wt %,about 70 wt %, about 75 wt %, about 80 wt %, or about 85 wt %, or withina range having any two of these values as endpoints, inclusive of theendpoints. In some embodiments, the amount of the polyurethane(s) in ablend can range from about 20 wt % to about 75 wt %, about 30 wt % toabout 65 wt %, or about 40 wt % to about 55 wt %.

In some embodiments, the blending temperature can range from about roomtemperature (18° C.) to about 100° C., including subranges. For example,the blend temperature can be about 18° C., about 30° C., about 40° C.,about 50° C., about 60° C., about 70° C., about 80° C., about 90° C., orabout 100° C., or within a range having any two of these values asendpoints, inclusive of the endpoints. In some embodiments, the blendtemperature can range from about 18° C. to about 90° C., about 18° C. toabout 80° C., about 18° C. to about 70° C., about 18° C. to about 60°C., about 18° C. to about 50° C., about 18° C. to about 40° C., or about18° C. to about 30° C.

In some embodiments, the blending time for step 1906 can range fromabout 15 minutes to about 3 hours, including subranges. For example, theblending time can be about 30 minutes, about 1 hour, about 90 minutes,about 2 hours, about 150 minutes, or about 3 hours, or within a rangehaving any two of these values as endpoints, inclusive of the endpoints.In some embodiments, the blending time can range from about 15 minutesto about 150 minutes, about 15 minutes to about 2 hours, about 15minutes to about 90 minutes, or about 15 minutes to about 1 hour. Insome embodiments, the blending speed for step 1906 can range from about150 rpm to about 250 rpm, including subranges. For example, the blendingspeed can be about 150 rpm, about 175 rpm, about 200 rpm, about 225 rpm,or about 250 rpm. In some embodiments, the blending speed can range fromabout 150 rpm to about 225 rpm, about 150 rpm to about 200 rpm, or about150 rpm to about 225 rpm. The blending speed can depend on the size of ablending device (e.g., size of an impeller) and/or the size of thevessel in which the components are blended.

In some embodiments, one or more additives can be added to the blend instep 1906. The additive(s) can influence the final properties of aprotein polyurethane alloy layer, and therefore the final properties ofa layered material 1700. For example, the additive(s) added can impactone or more of the following material properties: stiffness, elasticity,cohesive strength, tear strength, fire retardancy, chemical stability,or wet stability. Suitable additives include, but are not limited to,cross-linkers, fillers, dyes, pigments, plasticizers, waxes, rheologicalmodifiers, flame retardants, antimicrobial agents, antifungal agents,antioxidants, UV stabilizers, mechanical foaming agents, chemicalfoaming agents, foam stabilizers, and the like. Suitable dyes include,but are not limited to fiber reactive dyes or natural dyes. Suitablecross-linkers include, but are not limited to, epoxy-basedcross-linkers, (for example, poly(ethylene glycol) diglycidyl ether(PEGDE) available from Sigma Aldridge), isocyanate-based cross-linkers(for example, XTAN® available from Lanxess), and carbodiimide-basedcross-linkers. Suitable foaming agents include, HeiQ Chemtex 2216-T (astabilized blend of nonionic and anionic surfactants), HeiQ Chemtex2241-A (a modified HEUR (hydrophobically-modified ethylene oxideurethane) thickener), HeiQ Chemtex 2243 (a non-ionic siliconedispersion), or HeiQ Chemtex 2317 (a stabilized blend of nonionic andanionic surfactants) foam stabilizers available from HeiQ Chemtex.Suitable antimicrobial/antifungal agents include Ultra-Fresh DW-56, orother antimicrobial/antifungal agents used in the leather industry.Suitable flame retardants include CETAFLAM® DB9 (organophosphorouscompounds containing C—PO(OH)₂ or C—PO(OR)₂ groups with the carbon chaincontaining polymers), CETAFLAM® PD3300 (organophosphorous compoundscontaining C—PO(OH)₂ or C—PO(OR)₂ groups with the carbon chaincontaining polymers), or other flame retardants used for coatedtextiles. Suitable fillers include, but are not limited to,thermoplastic microspheres, for example, EXPANCEL® Microspheres.Suitable rheological modifiers include, but are not limited to, alkaliswellable rheological modifiers, hydrophobically-modified ethyleneoxide-based urethane (HEUR) rheological modifiers, and volume exclusionthickeners. Exemplary alkali swellable rheological modifiers include butare not limited to, ACRYSOL™ DR-106, ACRYSOL™ ASE-60 from Dow Chemicals,TEXICRYL® 13-3131, and TEXICRYL® 13-308 from Scott-Bader. Exemplary HEURmodifiers include, but are not limited to, RM-4410 from Stahl andChemtex 2241-A from HeiQ. Exemplary volume exclusion thickeners include,but are not limited to, WALOCEL™ XM 20000 PV from Dow Chemicals andMethyl-Hydroxyethyl Cellulose from Sigma-Aldrich.

In some embodiments, a blend can include one or more coloring agents. Insome embodiments, the coloring agent can be a dye, for example a fiberreactive dye, a direct dye, or a natural dye. Exemplary dyes, includebut are not limited to, Azo structure acid dyes, metal complex structureacid dyes, anthraquinone structure acid dyes, and azo/diazo direct dyes.In some embodiments, the coloring agent can be pigment, for example alake pigment. In some embodiments, a blend can include a coloring agentcontent of about 2 wt % or less. For example, a blend can include about0.1 wt %, about 0.5 wt %, about 1 wt %, about 1.5 wt %, or about 2 wt %coloring agent. In some embodiments, a blend can include about 0.1 wt %to about 2 wt %, about 0.5 wt % to about 1.5 wt %, or about 0.1 wt % toabout 1 wt % coloring agent. In some embodiments, a blend can be free orsubstantially free of a coloring agent. In such embodiments, a proteinpolyurethane alloy layer created from the blend can be free orsubstantially free of a coloring agent.

In step 1908, a layer of the blended mixture is disposed over topsurface 2002 of sacrificial layer 2000. The blended mixture can becoated over top surface 2002 of sacrificial layer 2000. In embodimentsnot including steps 1902 and 1904, the blended mixture can be coateddirectly on top surface 2002 of sacrificial layer 2000. In embodimentsincluding step 1904, the blended mixture can be coated directly on asurface of basecoat layer 1760. In embodiments including step 1902 butnot step 1904, the blended mixture can be coated directly on a surfaceof top-coat layer 1770. In some embodiments, the blended mixture can beformed into a sheet by coating it on a surface to a desired thickness.Coating can include pouring, extruding, casting, and the like. In someembodiments, the sheet can be spread to a desired thickness using, forexample, a blade, a knife, a roller, a knife over roll, curtain coating,and slot die coating.

In some embodiments, the temperature of the blended mixture duringcoating can be about 40° C. or higher. For example, the temperature ofthe blended mixture can range from about 40° C. to about 100° C.,including subranges. For example, the temperature can be about 40° C.,about 50° C., about 60° C., about 70° C., about 80° C., about 90° C., orabout 100° C., or within a range having any two of these values asendpoints, inclusive of the endpoints. In some embodiments, thetemperature of the blended mixture during coating can range from about40° C. to about 90° C., about 40° C. to about 80° C., about 40° C. toabout 70° C., about 40° C. to about 60° C., or about 40° C. to about 50°C. Coating at a temperature below about 40° C. can result in the blendedmixture being too viscous and can make it difficult to form a layer ofuniform thickness.

In step 1910, solvent (for example, water) can be removed from thecoated blended mixture to form protein polyurethane alloy layer 1720, asillustrated in for example, FIG. 20C. Suitable solvent removal methodsinclude, but are not limited to tunnel drying, vacuum drying, ovendrying with hot air, humidity chamber drying, flotation drying with hotair, and ovens with a combination of medium range IR (infrared) forpreheating and then hot air for subsequent drying.

Suitable solvent removal temperatures for step 1910 can range from aboutroom temperature (18° C.) to about 100° C., including subranges. Forexample, solvent may be removed at a temperature of about 18° C., about35° C., about 50° C., about 60° C., about 70 ° C., about 80° C., about90° C., or about 100° C., or within a range having any two of thesevalues as endpoints, inclusive of the endpoints. In some embodiments,solvent may be removed at a temperature ranging from about 18° C. toabout 35° C., about 18° C. to about 50° C., about 18° C. to about 60°C., about 18° C. to about 70° C., about 18° C. to about 80° C., about18° C. to about 90° C., or about 18° C. to about 100° C. Suitablehumidity values for solvent removal in step 1910 include a humidity in arange from 0% RH (relative humidity) to about 65% RH, includingsubranges. For example, the humidity can be about 10% RH, about 20% RH,about 40% RH, about 50% RH, or about 65% RH, or within a range havingany two of these values as endpoints, inclusive of the endpoints. Insome embodiments, the humidity can be 0% RH to about 50% RH, 0% RH toabout 40% RH, 0% RH to about 20% RH, or 0% RH to about 10% RH. Thesolvent removal temperature and/or humidity can affect the finalproperties of a protein polyurethane alloy layer, and therefore alayered material. The solvent removal temperature and/or humidity instep 1910 can impact one or more of the following material properties:stiffness, elasticity, cohesive strength, tear strength, fireretardancy, chemical stability, and wet stability. For example,relatively high humidity and relatively low temperature can result in amaterial that is softer and more elastic. Conversely, relatively lowhumidity and relatively high temperature can result in a material thatis harder and less elastic.

In some embodiments, steps 1906-1910 can be repeated a plurality oftimes to form a plurality of protein polyurethane alloy layers 1720 oversacrificial layer 2000. In some embodiments, steps 1906-1910 can berepeated sequentially to form a plurality of protein polyurethane alloylayers 1720 over sacrificial layer 2000. In some embodiments, steps1906-1910 can be repeated after steps 1912-1916 to form one or moreprotein polyurethane alloy layers 1720 over one or more foamed proteinpolyurethane alloy layers 1730/1740. In some embodiments, method 1900may not include steps 1906-1910.

In step 1912, one or more polyurethanes dispersed or dissolved in anaqueous solution can be blended with protein(s) and foamed to form afoamed blended mixture in the aqueous solution. In some embodiments, theone or more polyurethanes can be dispersed or dissolved in an aqueoussolution before blending with protein(s) and foaming. In someembodiments, the one or more polyurethanes can become dispersed ordissolved in an aqueous solution during blending with protein(s) andfoaming. In some embodiments, the one or more polyurethanes and the oneor more proteins can be blended in a suitable vessel until a homogenousblend is formed. Suitable blending equipment includes, but is notlimited to, a blender, a stand mixer, an in-line mixer, or a high shearmixer. The blend may be foamed using, for example, a mechanical foamingprocess or a chemical foaming process. Exemplary mechanical foamingequipment includes a Hansa Mixer or a GEMATA® foamer. Blending andfoaming can be performed separately or concurrently.

Suitable polyurethane(s) for blending and foaming in step 1912 are thosediscussed herein for protein polyurethane alloy layers. In someembodiments, one or more foaming agents and/or foam stabilizers may beadded to the blend in step 1912. Suitable foaming agents and foamstabilizers include those discussed herein for protein polyurethanealloy layers 1730/1740.

In some embodiments, a blend can include a foaming agent or a foamstabilizer content of about 10 wt % or less. For example, a blend caninclude about 0.1 wt %, about 1 wt %, about 2.5 wt %, about 5 wt %,about 7.5 wt %, or about 10 wt % foaming agent or foam stabilizer. Insome embodiments, a blend can include about 0.1 wt % to about 10 wt %,about 1 wt % to about 7.5 wt %, about 2.5 wt % to about 5 wt %, about0.1 wt % to about 5 wt %, or about 0.1 wt % to about 2.5 wt % foamingagent or foam stabilizer. In some embodiments, a blend can besubstantially free or free of a foaming agent and/or a foam stabilizer.In such embodiments, a protein polyurethane alloy layer created from theblend can be substantially free or free of a foaming agent and/or a foamstabilizer.

Foaming in step 1912 can be used to impart a desired density for afoamed protein polyurethane alloy layer. In some embodiments, a foamedblended mixture can have a liquid density, before solvent is removed instep 1916, ranging from about 300 g/L to about 900 g/L, includingsubranges. For example, a foamed blended mixture formed in step 1912 canhave a liquid density of about 300 g/L, about 400 g/L, about 500 g/L,about 600 g/L, about 700 g/L, about 800 g/L, or about 900 g/L, or withina range having any two of these values as endpoints. In someembodiments, the foamed blended mixture can have a liquid densityranging from about 300 g/L to about 800 g/L, about 300 g/L to about 700g/L, about 400 g/L to about 600 g/L, about 300 g/L to about 500 g/L, orabout 300 g/L to about 600 g/L. In some embodiments, a blended mixtureformed in step 1906 can have a liquid density, before the solvent isremoved from the blended mixture in step 1910 that is greater than theliquid density of the foamed blended mixture formed in step 1912 beforesolvent is removed in step 1916.

In some embodiments, protein(s) can be dispersed or dissolved in anaqueous solution before blending with polyurethane and foaming in step1912. Suitable aqueous solutions include those discussed above for step1906. The protein concentration in the aqueous solution can be any valueor range discussed above for step 1906. The amount of protein in aprotein/polyurethane blend for step 1912 can be any value or rangediscussed above for step 1906. The blending temperature for step 1912can be any temperature or temperature range discussed above for step1906. The blending time for step 1912 can be any time or time rangediscussed above for step 1906. The blending speed for step 1912 can beany speed or speed range discussed above for step 1906. In someembodiments, one or more additives can be added to the blend in step1912. The additive(s) added in step 1912 can be any of the additivesdiscussed above for step 1906.

In step 1914, a layer of the foamed blended mixture is disposed oversacrificial layer 2000. In some embodiments, a layer of the foamedblended mixture is disposed over a surface of a protein polyurethanealloy layer 1720. In some embodiments, the blended and foamed mixturecan be coated directly on a surface of a protein polyurethane alloylayer 1720. In some embodiments, the foamed blended mixture can beformed into a sheet by coating it on a surface to a desired thickness.Coating can include pouring, extruding, casting, and the like. In someembodiments, the sheet can be spread to a desired thickness using, forexample, a blade, a knife, a roller, a knife over roll, curtain coating,and slot die coating.

In step 1916, solvent (for example, water) can be removed from thecoated, foamed blended mixture to form a foamed protein polyurethanealloy layer 1730, as illustrated in for example, FIG. 20D. Suitablesolvent removal methods include, but are not limited to tunnel drying,vacuum drying, oven drying with hot air, humidity chamber drying,flotation drying with hot air, and ovens with a combination of mediumrange IR for preheating and then hot air for subsequent drying. Suitablesolvent removal temperatures for step 1916 can any of the temperature ortemperature ranges discussed above for step 1910. Humidity values forstep 1916 can be any of the humidity values or humidity ranges discussedabove for step 1910

In some embodiments, steps 1912-1916 can be repeated a plurality oftimes to form a plurality of foamed protein polyurethane alloy layersover sacrificial layer 2000, for example, foamed protein polyurethanealloy layers 1730 and 1740. In such embodiments, the foamed blendedmixtures formed in separate steps 1912 can have different liquiddensities. For example, the liquid density for one foamed blendedmixture can be 10 g/L to 300 g/L more or less than the liquid densityfor another foamed blended mixture. For example, in some embodiments, afirst blended mixture can have a liquid density ranging from about 300g/L to about 500 g/L and a second blended mixture can have a liquiddensity ranging from about 600 g/L to about 700 g/L. As another example,a first blended mixture can have a liquid density ranging from about 300g/L to about 400 g/L and a second blended mixture can have a liquiddensity ranging from about 500 g/L to about 700 g/L.

In some embodiments, steps 1912-1916 can be repeated sequentially toform a plurality of foamed protein polyurethane alloy layers oversacrificial layer 2000. In some embodiments, a foamed and blendedmixture formed in step 1912 can be used to form multiple foamed proteinpolyurethane alloy layers in steps 1914-1916. In some embodiments, steps1912-1916 can be performed before performing a set of steps 1906-1910 toform one or more foamed protein polyurethane alloy layers between aprotein polyurethane alloy layer 1720 and sacrificial layer 2000. Insome embodiments, method 1900 may not include steps 1912-1916.

In step 1918, sacrificial layer 2000 is removed from the layer(s) formedin steps 1902-1916, as illustrated in for example FIG. 20E. Sacrificiallayer 2000 can be removed by a mechanical process or a chemical process.For example, sacrificial layer 2000 can be removed by peelingsacrificial layer 2000 away from the other layers. As another example,sacrificial layer 2000 can be removed by dissolving sacrificial layer2000. In some embodiments, sacrificial layer 2000 can be removed in step1918 before attaching the layer(s) formed in steps 1902-1916 to asubstrate layer 1710 in step 1920. In some embodiments, sacrificiallayer 2000 can be removed after step 1920.

In step 1920, the layer(s) formed in steps 1902-1916 are attached to asubstrate layer 1710, as illustrated in for example FIG. 20F. In step1920, protein polyurethane alloy layer 1720, and any other proteinpolyurethane alloy layers formed in steps 1906-1916 are attached tosubstrate layer 1710. In some embodiments, attaching one or more proteinpolyurethane alloy layers (e.g., protein polyurethane alloy layer 1720)to substrate layer 1710 in step 1920 includes a heat pressing process.In such embodiments, protein polyurethane alloy layer (e.g., proteinpolyurethane alloy layer 1720) can be in direct contact with substratelayer 1710. Also, in such embodiments, a protein polyurethane alloylayer can partially melt into substrate layer 1710, and upon cooling thetwo layers are firmly attached. In some embodiments, attaching one ormore protein polyurethane alloy layers (e.g., protein polyurethane alloylayer 1720) to substrate layer 1710 in step 1920 includes a laminationprocess. In such embodiments, lamination can be accomplished with anadhesive layer 1750. In such embodiments, substrate layer 1710 and/or aprotein polyurethane alloy layer can be coated with an adhesive by knowntechniques such as slot die casting, kiss coating, a drawdown technique,or reverse transfer coating. In some embodiments, the lamination processcan include passing substrate layer 1710 and the other layer(s) throughrollers under heat.

In some embodiments, step 1920 can be omitted from method 1900. In suchembodiments, the layer(s) formed in steps 1902-1916 define a proteinpolyurethane alloy layer or a layered material without a substrate layer1710.

In some embodiments, layered materials described herein can have a tearstrength that is at least about 1% greater than that of a naturalleather of the same thickness. For example, the layered material canhave a tear strength that is about 1%, about 2%, about 3%, about 4%,about 5%, about 6%, about 7%, about 8%, about 9%, about 10%, about 15%,about 20%, about 25%, about 30%, about 35%, about 40%, about 45%, about50%, about 100%, about 150%, or about 200% greater than that of naturalleather of the same thickness. In some embodiments, the layered materialcan have a tear strength in the range of about 20 N to about 300 N,including subranges. For example, the tear strength of the layeredmaterial can be about 20 N, about 30 N, about 40 N, about 50 N, about 60N, about 70 N, about 80 N, about 90 N, about 100 N, about 125 N, about150 N, about 175 N, about 200 N, about 225 N, about 250 N, about 275 N,or about 300 N, or within a range having any two of these values asendpoints, inclusive of the endpoints. In some embodiments, the tearstrength can range from about 30 N to about 275 N, about 40 N to about250 N, about 50 N to about 225 N, about 60 N to about 200 N, or about 75N to about 175 N, about 80 N to about 150 N, about 90 N to about 125 N,or about 100 N to about 125 N.

In some embodiments, a protein polyurethane alloy layer described hereincan have a tear strength in the range of about 2 N to about 30 N,including subranges. For example, the tear strength of the proteinpolyurethane alloy layer can be about 2 N, about 4 N, about 5 N, about10 N, about 15 N, about 20 N, about 25 N, or about 30 N, or within arange having any two of these values as endpoints, inclusive of theendpoints. In some embodiments, the tear strength can range from about 4N to about 25 N, about 5 N to about 20 N, or about 10 N to about 15 N.

Tear strength, or tear resistance, is a measure of how well a materialcan withstand the effects of tearing. Tear resistance can be measured bya variety of methods, for example the method provided by ASTM D 412 orthe method provided by ISO 3377 (also called the “Bauman tear”). Themethod provided by ASTM D 624 can also be used to measure the resistanceto the formation of a tear and the resistance to the expansion of atear. Regardless of the method used, first, a cut is made in thematerial sample tested to induce a tear. Then, the sample is heldbetween two grips and a uniform pulling force is applied until sampletears in two. Tear resistance is then calculated by dividing the forceapplied by the thickness of the material. Unless specified otherwise, atear strength value reported herein is measured by ISO 3377.

In some embodiments, the layered materials described herein can have atensile strength in the range of about 1 kPa (kilopascal) to about 100MPa (megapascals), including subranges. For example, the layeredmaterial can have a tensile strength of about 1 kPa, about 50 kPa, about100 kPa, about 200 kPa, about 300 kPa, about 400 kPa, about 500 kPa,about 600 kPa, about 700 kPa, about 800 kPa, about 900 kPa, about 1 MPa,about 5 MPa, about 10 MPa, about 20 MPa, about 30 MPa, about 40 MPa,about 50 MPa, about 60 MPa, about 70 MPa, about 80 MPa, about 90 MPa, orabout 100 MPa, or within a range having any two of these values asendpoints, inclusive of the endpoints. In some embodiments, the tensilestrength can range from about 50 kPa to about 90 MPa, about 100 kPa toabout 80 MPa, about 200 kPa to about 70 MPa, about 300 kPa to about 60MPa, about 400 kPa to about 50 MPa, about 500 kPa to about 40 MPa, about600 kPa to about 30 MPa, about 700 kPa to about 20 MPa, about 800 kPa toabout 10 MPa, or about 1MPa to about 5 MPa.

Softness, also referred to as “hand feel” of a material can bedetermined by ISO 17235. In some embodiments, an exterior surface of alayered material described herein can have a softness ranging from about2 mm to about 12 mm, including subranges. For example, an exteriorsurface of a layered material can have a softness of about 2 mm, about 3mm, about 4 mm, about 5 mm, about 6 mm, about 7 mm, about 8 mm, about 9mm, about 10 mm, about 11 mm, or about 12 mm, or within a range havingany two of these values as endpoints, inclusive of the endpoints. Insome embodiments, the softness can be about 3 mm to about 11 mm, about 4mm to about 10 mm, about 5 mm to about 9 mm, about 6 mm to about 8 mm,or about 6 mm to about 7 mm. Unless specified otherwise, a softnessvalue disclosed herein is determined by ISO 17235.

Flexibility, or strain, of a material can be determined by measuring itselongation at failure when a tensile force is applied, for example usingthe equation: ΔT/L , where ΔL is the change in length of the materialafter the tensile force is applied, and L is the original length of thematerial. Flexibility can also be measured according to the methodprovided by ASTM D 412. In some embodiments, the layered materialsdescribed herein can have a flexibility in the range of about 100% toabout 400%, including subranges. For example, the layered materials canhave a flexibility of about 100%, about 200%, about 300%, or about 400%,or within a range having any two of these values as endpoints, inclusiveof the endpoints. In some embodiments, the flexibility can be about 100%to about 200%, about 100% to about 300%, about 200% to about 300%, orabout 200% to about 400%. Unless specified otherwise, a flexibilityvalue disclosed herein is measured by ASTM D 412. In some embodiments, aprotein polyurethane alloy layer described herein can have flexibilityvalue or range as described above for a layered material.

In some embodiments, a layered material as described herein can have apermanent set in a hysteresis experiment of about 8% or less. In someembodiments, a layered material can have a permanent set of about 1%,about 2%, about 3%, about 4%, about 5%, about 6%, about 7%, or about 8%,or within a range having any two of these values as endpoints. In someembodiments, a layered material can have a permanent set of about 1% toabout 8%, about 2% to about 7%, about 3% to about 6%, or about 4% toabout 5%.

Unless specified otherwise, a permanent set value is measured by thefollowing method. A dog-bone-shaped tensile specimen of a material iscut and the original length of the sample is measured. The samples arecut to have a dog-bone shape with about 110 mm length and 10 mm width(75-100 mm gauge length). Then, the sample is stretched along its lengthusing an INSTRON® machine to 15% strain and returned to 0% strain, bothat a constant rate of three millimeters per second. This is repeatedfive times. Then, the distance between the original sample length andthe length of the sample at which the load goes to zero on the lastreturn cycle is measured. The percent difference between the lengthmeasured after repeatedly straining the material and the original lengthis the permanent set %. For purposes of calculating a permanent setvalue, three separate samples of a material are evaluated, and theaverage permanent set value is reported as the permanent set value forthe material.

In some embodiments, layered materials described herein can have amoisture vapor transmission rate (MVTR) of about 75 g/m²/hr or more. Insome embodiments, layered materials described herein can have a MVTRranging from about 75 g/m²/hr to about 200 g/m²/hr, including subranges.For example, the layered material can have a MVTR of about 80 g/m²/hr toabout 190 g/m²/hr, about 90 g/m²/hr to about 180 g/m²/hr, about 100g/m²/hr to about 170 g/m²/hr, about 110 g/m²/hr to about 160 g/m²/hr,about 120 g/m²/hr to about 150 g/m²/hr, or about 130 g/m²/hr to about140 g/m²/hr. Unless specified otherwise, a MVTR value disclosed hereinis measured using ASTM E96 (“Standard Test Methods for Water VaporTransmission of Materials”)—Procedure B, Water Method, at about 74.3°F., at about 50% relative humidity, and with a ¾ inch air gap.

Layered materials having a moisture vapor transmission rate as reportedherein can be suitable for use in a variety of applications wherebreathability of the material is a desirable property. Exemplaryapplications where breathability can be desirable include, but are notlimited to, footwear, apparel, and upholstery. Layered materials asdescribed herein can have a significantly higher water vaportransmission rate compared to a layered polymeric material having thesame number of layers with the same thicknesses and made of the samepolymeric material(s), but without protein blended in the polymericmaterial(s).

In some embodiments, layered materials described herein can have a colorfastness of class 4 or higher when measured according to ISO 11640(“Leather—Tests for color fastness—fastness to cycles of to-and-frorubbing”) wet-rub fastness test. In some embodiments, layered materialsdescribed herein can have a color fastness of class 4, class 4.5, orclass 5 when measured according to ISO 11640's wet-rub fastness test. Acolor fastness of class 4 or higher can provide layered materialsdescribed herein with desirable wear resistance for a variety ofapplications.

Layered materials described herein can achieve a color fastness of class4 or higher without the inclusion of a pigment in the materials. This isa unique characteristic compared to a layered polyurethane material madeof the same polyurethane(s) without protein(s) blended in thepolyurethane(s). Protein within layered materials described herein canadhere well to a dye used to color the material. To achieve a high colorfastness, polyurethane materials are usually colored using a pigmentbecause dyes do not generally adhere to a polyurethane well. Pooradherence between a dye and a polyurethane leads to a relatively lowcolor fastness. Dyed layered materials described herein can haveimproved depth of color and other aesthetic features not achievable witha polyurethane colored using a pigment.

In some embodiments, a layered material described herein, or anindividual layer of a layered material described herein, can besubjected to the same, or similar finishing treatments as those used totreat natural leather. In some embodiments, a layered material describedherein can be tumbled or staked to tailor properties of the material,such as the feel of the material. In such embodiments, traditionaltextile tumbling and staking methods can be used.

In some embodiments, a layered material, or an individual layer of alayered material, can have a rough exterior surface. For example, topsurface 1724 of protein polyurethane alloy layer 1720 can have a roughsurface, top surface 1774 of top-coat layer 1770 can have a roughsurface, top surface 1764 of basecoat layer 1760 can have a roughsurface, top surface 1734 of protein polyurethane alloy layer 1730 canhave a rough surface, or top surface 1744 of protein polyurethane alloylayer 1740 can have a rough surface. A rough exterior surface can createa surface texture similar in appearance and feel to that of a naturelleather (e.g., the grain of pebbled natural leather). In someembodiments, top surface 2002 of sacrificial layer 2000 can have a roughsurface that is transferred onto the surface of a layer disposeddirectly on top surface 2002 during method 1900.

A rough surface has a surface area per square inch of at least about 1%greater than 1 in². In other words, in some embodiments, a one squareinch sample of layered material 1700, including a layer having roughexterior surface, can have a surface area that is at least about 1%greater than a one square inch sample of a material having a perfectlysmooth surface. In some embodiments, a rough exterior surface can have asurface area per square inch of at least about 1% greater than 1 in²,about 10% greater than 1 in², about 20% greater than 1 in², about 30%greater than 1 in², about 40% greater than 1 in², about 50% greater than1 in², about 60% greater than 1 in², about 70% greater than 1 in², about80% greater than 1 in², about 90% greater than 1 in², about 100% greaterthan 1 in², about 150% greater than 1 in², about 200% greater than 1in², about 250% greater than 1 in², about 300% greater than 1 in², about350% greater than 1 in², about 400% greater than 1 in², about 450%greater than 1 in², or about 500% greater than 1 in², or within a rangehaving any two of these values as endpoints, inclusive of the endpoints.In some embodiments, a rough surface can have a surface area per squareinch of about 1% greater than 1 in² to about 500% greater than 1 in²,about 10% greater than 1 in² to about 450% greater than 1 in², about 20%greater than 1 in² to about 400% greater than 1 in², about 30% greaterthan 1 in² to about 350% greater than 1 in², about 40% greater than 1in² to about 300% greater than 1 in², about 50% greater than 1 in² toabout 250% greater than 1 in², about 60% greater than 1 in² to about200% greater than 1 in², about 70% greater than 1 in² to about 150%greater than 1 in², or about 80% greater than 1 in² to about 100%greater than 1 in². Unless specified otherwise, a surface area ofmaterial disclosed herein is measured using profilometry. Fornon-transparent materials, optical profilometry is used. In someembodiments, a layered material, or an individual layer of a layeredmaterial, can have a smooth exterior surface. A smooth surface has asurface area per square inch of less than 1% greater than 1 in². Forexample, a smooth surface can have a surface area per square inch of 1in² to less than 1.01 in². In some embodiments, top surface 2002 ofsacrificial layer 2000 can have a smooth surface that is transferredonto the surface of a layer disposed directly on top surface 2002 duringmethod 1900.

In some embodiments, a layered material, or an individual layer of alayered material, can have a textured exterior surface. In someembodiments, top surface 2002 of sacrificial layer 2000 can have atextured surface that is transferred onto the surface of a layerdisposed directly on top surface 2002 during method 1900. In someembodiments, a textured exterior surface can a surface area per squareinch, or surface area per square inch range, as discussed above for arough surface.

In some embodiments, the texture can be a macro-scale texture, forexample, any of the many textures used on Sappi/Warren Release Papersthat are commercially available under the trademark ULTRACAST® ortradename Classic, manufactured by S.D. Warren Company d/b/a Sappi NorthAmerica. An example of a macro-scale texture is a replicate of a naturalleather grain with feature depths of about 50 to about 300 microns. Anyother desired macro-scale texture may also be used. In some embodiments,a macro-scale texture can be a “leather grain texture.” As used herein,the term “leather grain texture” is a texture that mimics the look andfeel of natural leather. Exemplary “leather grain textures” include butare not limited to, Sappi Matte Freeport 189, Sappi Freeport 123, orSappi Expresso 904.

In some embodiments, the texture can be a micro-scale texture. In someembodiments, the texture can be a micro-scale texture with surfacefeatures having a feature size of less than 50 microns, for example 1000nanometers to less than 50 microns. An example of a micro-scale textureis referred to in the art as “Sharklet.” Sharklet textures can beapplied to provide the products with a surface that is structured toimpede bacterial growth. The micro-scale texture of the surfacereplicates sharkskin denticles, which are arranged in a diamond patternwith millions of tiny ribs. Sharklet materials are discussed, forexample, in U.S. Pat. Nos. 7,650,848 and 8,997,672, the disclosures ofwhich are incorporated herein by reference.

In some embodiments, the texture can be a nanoscale texture with surfacefeatures having a feature size of less than 1000 nanometers, for example10 nanometers to less than 1000 nanometers. One example of a nanoscaletexture is a diffraction grating that has a series of raised ridgesabout 400 nanometers wide, spaced approximately 800 nanometers apart,with a depth of approximately 100 nanometers.

The embodiments discussed herein will be further clarified in thefollowing examples. It should be understood that these examples are notlimiting to the embodiments described above.

EXAMPLE 1

A sample was prepared by mixing 5.5 g of a waterborne polyurethanedispersion L3360 from Hauthaway, with 10 mL of de-ionized water andstirring at 1000 rpm (rotations per minute) for 30 minutes at 50° C. Thesolution was then pipetted into a Teflon evaporating dish with adiameter of 10 cm. The dish was dried in an oven at 45° C. overnight.After drying, the dried sample was conditioned at standard referenceatmosphere (23° C., 50% humidity) for 24 hours, resulting in apolyurethane film.

The film was tested using a DMA-850 from TA Instruments. A 1 cm×2.5 cmstrip was cut from each film using a metal die. The cut film sampleswere loaded into the film and fiber tension clamp for testing. Duringtesting, a pre-load of 0.01 N was applied to the cut film samples. Theinstrument was cooled to −80° C., held for 1 minute, then thetemperature was ramped at 4° C/minute to 200° C., or until the samplewas too weak to be held in tension. During the temperature ramp, thesample was oscillated 0.1% strain at a frequency of 1 Hz. The storagemodulus, loss modulus, and tan(δ) were plotted with temperature for bothfilms. The resulting second storage modulus transition (taken as theonset point of the last decrease in the storage modulus measured, i.e.second DMA modulus transition onset temperature) was 114.9° C. for thecontrol sample.

Additionally, 5 tensile specimens (according to ASTM D638) were each cutfrom the dried and conditioned sample film using a metal die. The cutfilm samples were loaded into an INSTRON® 5960 series machine and pulledin tension at 100 millimeters/minute until break. The average Young'smodulus, average tensile strength (maximum tensile stress), and averageelongation at break were recorded. The Young's modulus was 59 MPa, themaximum tensile stress was 12.9 MPa, and the elongation at break was402%.

EXAMPLES 2-8

Examples 2-8 were performed using the same method as Example 1 to show arange of polyurethane dispersions. The polyurethanes used and theresulting properties are listed in Tables 3-6.

EXAMPLE 9

A sample was prepared by dissolving 0.825 g (grams) of gelatin fromporcine skin into 10 mL (milliliters) of de-ionized water and stirringwith a magnetic stir bar at 1000 rpm (rotations per minute) for 1 hourat 50° C. After the gelatin was fully dissolved, the pH of the solutionwas adjusted to 7.0 with 0.1 N sodium hydroxide. Then 5.5 g of L3360 wasadded to the solution and stirred at 1000 rpm for 30 minutes. Thepolyurethane and gelatin solution was then pipetted into a Teflonevaporating dish with a diameter of 10 cm. The dish was dried in an ovenat 45° C. overnight. After drying, the dried sample was conditioned atstandard reference atmosphere (23° C., 50% humidity) for 24 hours tocreate a gelatin polyurethane alloy film.

At the time of pipetting, the gelatin polyurethane solution was milky inappearance, with no particulates visible. After drying, the gelatinpolyurethane solution produced a transparent film with uniform look withno optically visible granules. This result, combined with the Examplesof 33 and 34, show that when the protein is miscible with the hardphase, the protein polyurethane alloy can be transparent and haveenhanced properties.

DMA testing was performed as outlined in Example 1. The resulting secondstorage modulus transition (taken as the onset point of the lastdecrease in the storage modulus measured, i.e. second DMA modulustransition onset temperature) for the gelatin polyurethane alloy was180.6° C., a 65.7° C. increase over the control sample described inExample 1.

Tensile testing was performed as outlined in Example 1. The averageYoung's modulus was 344 MPa, the average tensile stress measured was19.8 MPa, and the average elongation at break was 197% for the gelatinpolyurethane alloy.

The increase in the second DMA modulus transition onset temperature ofthis example, along with increased modulus and strength, and decreasedelongation, compared to the polyurethane alone in Example 1, indicatethat the dissolved gelatin in the gelatin polyurethane alloy is misciblewith the hard phase of the polyurethane.

EXAMPLES 10-19

Examples 10-19 were performed using the same method as used for Example9 to show a range of polyurethane dispersions from differentmanufacturers and different proteins. The resulting properties of thesealloys are listed in Tables 3-6.

EXAMPLE 20

A sample was prepared by dissolving 0.825 g (grams) of Bovine SerumAlbumin from Sigma (BSA) into 10 mL (milliliters) of de-ionized waterand stirring with a magnetic stir bar at 1000 rpm (rotations per minute)for 1 hour at 20° C. Then 5.5 g of L3360 was added to the solution andstirred at 1000 rpm for 30 minutes. The polyurethane and BSA solutionwas then pipetted into a Teflon evaporating dish with a diameter of 10cm. The dish was dried on the benchtop at 25° C. overnight. Afterdrying, the dried sample was conditioned at standard referenceatmosphere (23° C., 50% humidity) for 24 hours to create a BSApolyurethane alloy film.

DMA testing was performed as outlined in Example 1. The resulting secondstorage modulus transition (taken as the onset point of the lastdecrease in the storage modulus measured, i.e. second DMA modulustransition onset temperature) for the BSA polyurethane alloy was 184.9°C., a 70° C. increase over the control sample described in Example 1.

Tensile testing was performed as outlined in Example 1. The averageYoung's modulus was 174 MPa, the average tensile stress measured was11.7 MPa, and the average elongation at break was 123% for the BSApolyurethane alloy.

EXAMPLE 21

Soy protein isolate (SPI) was dispersed by adding 0.75 g SPI into 15 mLof a sodium hydroxide solution at a 0.05 mol/L concentration. Thedispersion was stirred with a magnetic stir bar at 600 rpm for 3 hoursat 80° C. Then 5 g of L3360 was added to the solution and stirred at 600rpm for 30 minutes. The SPI polyurethane solution was then pipetted intoa Teflon evaporating dish with a diameter of 10 cm. The dish was driedin an oven at 45° C. overnight. After drying, the dried sample wasconditioned at standard reference atmosphere (23° C., 50% humidity) for24 hours to create a SPI polyurethane alloy film.

DMA testing was performed as outlined in Example 1. The resulting secondstorage modulus transition (taken as the onset point of the lastdecrease in the storage modulus measured, i.e. second DMA modulustransition onset temperature) for the SPI polyurethane alloy was 186.6°C., a 72° C. increase over the control in Example 1.

Tensile testing was performed as outlined in Example 1. The averageYoung's modulus was 396 MPa, the average tensile stress measured was 18MPa, and the average elongation at break was 151% for the SPIpolyurethane alloy.

The increase in the second DMA modulus transition onset temperature,along with increased modulus and strength, and decreased elongation,indicate that the dissolved SPI in the SPI polyurethane alloy ismiscible with the hard phase of the polyurethane.

EXAMPLES 22-23

Examples 22-23 were preformed using the same method as Example 21. Theproteins used and the resulting properties of these protein polymeralloys are listed in Tables 3-6.

EXAMPLES 24-29

Samples were prepared by the same method as Example 9. The gelatin andL3360 amounts were varied to achieve various mass ratios of the twocomponents in the alloy samples. The masses of gelatin and PUdispersion, as well as the resulting mass fractions, are summarizedbelow in Table 2.

TABLE 2 Gelatin L3360 Dispersion Gelatin Mass L3360 Mass Ex. No. Added(g) Added (g) Fraction Fraction 24 1.25 3.6 50% 50% 25 0.5 5.7 20% 80%26 0.375 6.1 15% 85% 27 0.25 6.4 10% 90% 28 0.125 6.8  5% 95% 29 0.0257.1  1% 99%

Tensile and DMA testing were performed as outlined in Example 1. Theresulting properties of the alloys are listed in Tables 3-6.

EXAMPLE 30

Soy protein isolate (SPI) was dispersed by adding 0.25 g SPI into 15 mLof DI Water.

The dispersion was stirred with a magnetic stir bar at 600 rpm for 3hours at 80° C. Then 6.42 g of L3360 was added to the solution andstirred at 600 rpm for 30 minutes. The SPI polyurethane solution wasthen pipetted into a Teflon evaporating dish with a diameter of 10 cm.The dish was dried in an oven at 45° C. overnight. After drying, thedried sample was conditioned at standard reference atmosphere (23° C.,50% humidity) for 24 hours to create a SPI polyurethane alloy film.

Tensile and DMA testing were performed as outlined in Example 1. Theresulting properties of the alloy are listed in Tables 3-6.

EXAMPLE 31

Soy protein isolate (SPI) was dispersed by adding 0.5 g SPI into 15 mLof a sodium hydroxide solution at a 0.05 mol/L concentration. Thedispersion was stirred with a magnetic stir bar at 600 rpm for 3 hoursat 80° C. Then 6.42 g of L3360 was added to the solution and stirred at600 rpm for 30 minutes. The SPI polyurethane solution was then pipettedinto a Teflon evaporating dish with a diameter of 10 cm. The dish wasdried in an oven at 45° C. overnight. After drying, the dried sample wasconditioned at standard reference atmosphere (23° C., 50% humidity) for24 hours to create a SPI polyurethane alloy film.

Tensile and DMA testing were performed as outlined in Example 1. Theresulting properties of the alloy are listed in Tables 3-6.

EXAMPLE 32

Whey protein (bovine milk whey W1500 from Sigma) was dispersed by adding0.75 g Whey into 15 mL of a sodium hydroxide solution at a 0.05 mol/Lconcentration. The dispersion was stirred with a magnetic stir bar at600 rpm for 3 hours at 80° C. Then 5 g of L3360 was added to thesolution and stirred at 600 rpm for 30 minutes. The whey polyurethanesolution was then pipetted into a Teflon evaporating dish with adiameter of 10 cm. The dish was dried in an oven at 45° C. overnight.After drying, the dried sample was conditioned at standard referenceatmosphere (23° C., 50% humidity) for 24 hours to create a wheypolyurethane alloy film.

DMA testing was performed as outlined in Example 1. The resulting secondstorage modulus transition (taken as the onset point of the lastdecrease in the storage modulus measured, i.e. second DMA modulustransition onset temperature) for the whey polyurethane alloy was 100.9°C., a 14° C. decrease compared to the control in Example 1.

Tensile testing was performed as outlined in Example 1. The averageYoung's modulus was 105 MPa, the average tensile stress measured was 7.6MPa, and the average elongation at break was 224% for the wheypolyurethane alloy.

While the whey appears to be miscible with the hard phase of thepolyurethane, it is believed that the second DMA modulus transitiontemperature did not increase because of the poor thermal stability ofthe protein itself. As discussed above, the whey had a denaturationtemperature at 158° C., and was therefore considered non-thermo-stable.

EXAMPLE 33

0.75 g of casein (from bovine milk, Sigma, C7078) was added into 15 mLof DI water (pH=7) in a 20 mL glass vial without any other additives,stirred at 600 rpm, heated to 90° C., and maintained for 3 hours.

Then 5 g of L3360 was added into the 20 mL glass vial. The glass vialwas capped and vortexed for 1 min at max speed. The mixed caseinpolyurethane liquid was then transferred into a 10 cm Teflon dish. Thedish was dried in an oven at 45° C. overnight (16 to 24 hours).

After drying, the casein polyurethane alloy film had an opaque look withnumerous optically visible granules in the film. The tensile propertiesof this film were measured by measuring five tensile specimens using anINSTRON° 5960 series machine. The samples were pulled in tension at 100millimeters/minute until break. The average tensile strength for thefilm was 4.96 MPa. The average elongation at break for the film was12.03%. The average Young's modulus of the film was 158 MPa. Theseresults, along with the results of Example 39, indicate that casein isinsoluble and not dispersible in water at pH 7, and thus does notdissolve in L3360 when mixed.

EXAMPLE 34

0.75 g of casein (from bovine milk, Sigma, C7078) was dispersed into a15 mL 0.05 mol/L NaOH DI water solution in a 20 mL glass vial, stirredat 600 rpm, heated to 90° C., and maintained for 3 hours. A uniformdispersion was obtained.

Then 5 g of L3360 was added into the 20 mL glass vial. The glass vialwas then capped and vortexed for 1 min at max speed. The mixed caseinpolyurethane liquid was then transferred into a 10 cm Teflon dish. Thedish was dried in an oven at 45° C. overnight (16 to 24 hours).

After drying, the casein polyurethane alloy film had a transparent anduniform look with no optically visible granules in the film. The tensileproperties of this film were measured by measuring five tensilespecimens using an INSTRON® 5960 series machine. The samples were pulledin tension at 100 millimeters/minute until break. The average tensilestrength for the film was 15.5 MPa. The average elongation at break forthe film was 160%. The average Young's modulus of the film was 160 MPa.The increase modulus, strength, and elongation compared to Example 33indicate that the modified casein dissolved within the polyurethane andis miscible with the hard phase of the polyurethane.

EXAMPLE 35

0.375 g of soy protein isolate (SPI) and 0.375 g r-Collagen were addedinto 15 mL of a sodium hydroxide solution at a 0.05 mol/L concentrationin a 20 mL glass vial. The soy protein isolate was soy protein isolatepurchased from MP Medicals (IC90545625). The r-Collagen was recombinantcollagen from Modern Meadow. The solution in the vial was mixed with amagnetic stir bar at 600 rpm for 2 hours at 80° C.

Then 5 g of L3360 was added into the 20 mL glass vial. The glass vialwas capped and vortexed for 1 min at max speed. The mixed SPI/r-colpolyurethane liquid was then transferred into a 10 cm Teflon dish. Thedish was dried in an oven at 45° C. overnight. After drying, the driedsample was conditioned at standard reference atmosphere (23° C., 50%humidity) for 24 hours to create a SPI/r-col polyurethane alloy film.

The tensile properties of this film were measured by measuring fivetensile specimens using an INSTRON® 5960 series machine. The sampleswere pulled in tension at 100 millimeters/minute until break. Theaverage tensile strength for the film was 15.71 MPa. The averageelongation at break for the film was 175.9%. The average Young's modulusof the film was 247.1 MPa. The film was also tested using a DMA-850 fromTA Instruments follow the method described in Example 1. The resultingsecond storage modulus transition (taken as the onset point of the lastdecrease in the storage modulus measured, i.e. second DMA modulustransition onset temperature) for the SPI/r-col polyurethane alloy was184.9° C.

Compared with Example No. 1 and Example No. 9, these results show theincrease in the second DMA modulus transition onset temperature, alongwith increased modulus and strength, and decreased elongation, indicatethat the blend of SPI and r-col in the polyurethane alloy was misciblewith the hard phase of the polyurethane and showed the correspondingenhancement in properties.

EXAMPLE 37

Using the same method as Example 36, a film was made with 0.375 g peaprotein MTX5232 from Bobs Red Mills, 0.375 g r-Collagen (recombinantcollagen from Modern Meadow) and 5 g of L3360 polyurethane dispersion.

The resulting protein polyurethane alloy film was tested using the sametensile and DMA testing methods as described for Example 36. The averagetensile strength for the film was 15.36 MPa. The average elongation atbreak for the film was 183.17%. The average Young's modulus of the filmwas 231.13 MPa. The second DMA modulus transition onset temperature forthe pea protein/r-col polyurethane alloy was 189.65° C.

Compared with Example No. 1 and Example No. 9, these results show theincrease in the second DMA modulus transition onset temperature, alongwith increased modulus and strength indicate that the blend of peaprotein and r-col in the protein polyurethane alloy was miscible withthe hard phase of the polyurethane and showed the correspondingenhancement in properties.

EXAMPLE 38

A gelatin solution was prepared by dissolving 0.825 g (grams) of gelatinfrom porcine skin (Sigma Aldrich G2500) into 10 mL (milliliters) ofde-ionized water and stirring with a magnetic stir bar at 1000 rpm(rotations per minute) for 1 hour at 50° C. After the gelatin was fullydissolved, the pH of the solution was adjusted to 7.0 with 0.1 N sodiumhydroxide. Navy Black #1684 fiber reactive dye was added to the gelatinsolution at 4.05 parts per hundred parts of gelatin and mixed for 15minutes at 45° C. Then 5.5 g of L3360 was added to the solution andstirred at 1000 rpm for 30 minutes. The polyurethane and gelatinsolution was then pipetted into a Teflon evaporating dish with adiameter of 10 cm. The dish was dried in an oven at 45° C. overnight.The resulting film was evenly dyed, with no phase separation ordifference in color across the sample. A comparable film of the samepolyurethane dispersion without protein could not be evenly dyed.

EXAMPLE 39A

Chemically modified soy protein solutions (chemically modified SUPRO® XT55 soy protein isolate and chemically modified SUPRO® XT 221D soyprotein isolate) were prepared by preparing two 5 mL of 0.1 mol/L sodiumhydroxide solutions. Once prepared, 40 milligrams (mg) of DABCO(1,4-diazabicyclo[2.2.2]octane) was added to each solution and allowedto dissolve. Upon dissolution of the DABCO, 300 mg of poly(ethyleneglycol) monoglycidyl ether-550 Mn was added to each solution followed bythe addition of 0.75 g of SUPRO® XT 55 soy protein isolate to onesolution and 0.75 g of SUPRO® XT 221D soy protein isolate to the othersolution. The solutions were allowed to stir at 600 rpm for 45 minutesat 65° C. to create chemically modified soy proteins with much highersolubility in an aqueous solution compared to the individual soyproteins in 0.1 mol/L sodium hydroxide alone without modification. Thepoly(ethylene glycol) monoglycidyl ether modified protein solutions weresignificantly more transparent compared to identical protein solutionswithout poly(ethylene glycol) monoglycidyl ether, indicating an increasein solubility. Additionally, size-exclusion chromatography (SEC) dataindicated that the soluble modified protein solutions showed minimalhydrolysis, indicating that the protein solubility was due to theprotein modification and not due to hydrolysis by the basic conditionsthat were used

EXAMPLE 39B

Chemically modified soy protein solutions (chemically modified SUPRO® XT55 soy protein isolate and chemically modified SUPRO® XT 221D soyprotein isolate) were prepared by preparing two 5 mL of 0.1 mol/L sodiumhydroxide solution. Once prepared, 40 mg of DABCO(1,4-diazabicyclo[2.2.2]octane) was added to each solution and allowedto dissolve. Upon dissolution of the DABCO, 300 mg of poly(ethyleneglycol) diglycidly ether-550 Mn was added to the solution followed bythe addition of 0.75 g SUPRO® XT 55 soy protein isolate to one solutionand 0.75 g of SUPRO® XT 221D soy protein isolate to the other solution.The solutions were allowed to stir at 600 rpm for 45 minutes at 65° C.to create soy proteins with much higher solubility in an aqueoussolution compared to the individual soy proteins in 0.1 mol/L sodiumhydroxide alone without modification. The poly(ethylene glycol)diglycidyl ether modified protein solutions were significantly moretransparent compared to identical protein solutions withoutpoly(ethylene glycol) diglycidyl ether indicating an increase insolubility. Additionally, SEC data indicated that the soluble modifiedsoy protein solutions showed minimal hydrolysis, indicating that theprotein solubility was due to the protein modification and not due tohydrolysis by the basic conditions that were used.

EXAMPLE 40

SUPRO® XT55 soy protein isolate (SPI) was dispersed by adding 0.75 g SPIinto 5 mL of a sodium hydroxide solution at a 0.1 mol/L concentration.The dispersion was stirred with a magnetic stir bar at 600 rpm for 2hours at 65° C. HeiQ Chemtex 2317 (an anionic surfactant) was added inan amount of 5 parts per 100 parts protein by mass. Then 5 g of L3360was added to the solution and stirred at 600 rpm for 30 minutes. The SPIpolyurethane solution was then pipetted into a Teflon evaporating dishwith a diameter of 10 cm. The dish was dried in an oven at 45° C.overnight. After drying, the dried sample was conditioned at standardreference atmosphere (23° C., 50% humidity) for 24 hours to create a SPIpolyurethane alloy film.

EXAMPLE 41

A gelatin solution was prepared by dissolving 3.885 g of gelatin fromporcine skin (Sigma Aldrich G2500) into 22 mL de-ionized water andstirring at 450 rpm using an overhead impeller mixer for 1 hour at 50°C. After the gelatin was fully dissolved, the pH of the solution wasadjusted to 7.0 with 1 N sodium hydroxide. After the pH adjustment,antimicrobial Ultra-Fresh DW-56 was added at 1.2 parts per hundred partsof gelatin solution by weight. The solution was then mixed for 10minutes at 50° C. to assure good dispersion of all the components. After10 minutes, 15 mL of the solution was aliquoted and Antifoam 204 (amixture of organic polyether dispersions from Sigma Aldrich) was addedat 0.5 parts per hundred parts of the estimated final solution weight.The aliquoted solution was mixed for 10 minutes at 50° C. to assure gooddispersion of all the components. Then, 25.885 g L3360 was added to thesolution. After the addition of L3360, the solution was mixed until atemperature of 43° C. to 45° C. was reached.

To the other aliquot of the solution, HeiQ Chemtex 2216-T (a stabilizedblend of nonionic and anionic surfactants) at 5.5 parts per hundredsparts and HeiQ Chemtex 2317 (a stabilized blend of nonionic and anionicsurfactants) at 2.2 parts per hundreds parts of the solution weight wereadded along with 0.1 parts per hundreds parts of HeiQ Chemtex 2243 (anon-ionic silicone dispersion). The solution was then mechanicallyfrothed cold until wet densities between 650 g/L to 850 g/L at atemperature of 43° C. to 45° C. were reached, thereby forming a foamedblended mixture.

A surface finish comprising a top-coat and basecoat was prepared tocreate the pre-skin of the protein polyurethane alloy. A top-coat blendwas created by blending 9.74 parts of Stahl Melio WF-5227. A LIQ, 100parts of Stahl WT-42-511, 30 parts of Stahl DI-17-701, 30 parts of StahlXR-13-820, and 25 parts of water. A basecoat blend was created byblending 450 parts of Stahl RC-43-023, 50 parts of Stahl RU-3901, 150parts of Stahl RA-30, 50 parts of Stahl FI-1208, 30 parts of StahlXR-13-820, and 100 parts of Stahl RA-22-063.

The blended non-foamed solution was deposited on the dried pre-skinusing a drawdown device at a target wet thickness of 200 gsm and driedfor 15 minutes in a Mathis LTE-S Labcoater at 75° C., 2000 rpm airspeed, and 70% of the air blowing from underneath the sample to form aprotein polyurethane alloy layer. After this first layer was dried, asecond layer of the blended foamed solution was deposited on top of thefirst layer at the target wet thickness of 350 gsm and dried for 15minutes in a Mathis LTE-S Labcoater with a ramp-like drying procedurestarting at 75° C. for 5 minutes, then 100° C. for 5 minutes and lastly,120° C. for 5 minutes at 700 rpm air speed, and 70% of the air blowingfrom underneath to form a first foamed protein polyurethane alloy layer.After the foam layer was dried, a third layer of the blended foamedsolution was deposited on top of the first foamed layer at the targetwet thickness of 350 gsm and dried for 15 minutes in a Mathis LTE-SLabcoater with a ramp-like drying procedure starting at 75° C. for 5minutes, then 100° C. for 5 minutes and lastly, 120° C., 700 rpm airspeed, and 70% of the air blowing from underneath to form a secondfoamed protein polyurethane alloy layer.

After the sample was fully dried and conditioned for 24 hours in aconditioning chamber at 23° C. and 50% humidity for 24 hours, the samplewas cut and tested according to the DMA and tensile mechanical propertytests described herein. The resulting second storage modulus transition(taken as the onset point of the last decrease in the storage modulusmeasured, i.e. second DMA modulus transition onset temperature) was 190°C., the Young's modulus was 88.9 MPa, the tensile stress was 5.4 MPa,and the elongation at break was 110%.

EXAMPLE 42

A sample was prepared by dissolving 1 g of 50 KDa rCol into 5 mL ofde-ionized water and stirring with a magnetic stir bar at 1000 rpm for 1hour at 20° C. The 50 KDa rCol protein was a collagen fragment preparedby Modern Meadow comprising the amino acid sequence listed as SEQ IDNO: 1. After stirring for 1 hour, 6.7 g of L3360 was added to thesolution and stirred at 1000 rpm for 30 minutes. The polyurethane and 50KDa rCol solution was then pipetted into a Teflon evaporating dish witha diameter of 10 cm. The dish was dried in an oven at 45° C. overnight.After drying, the dried sample was conditioned at standard referenceatmosphere (23° C., 50% humidity) for 24 hours to create a 50 KDa rColpolyurethane alloy film.

DMA testing was performed as outlined in Example 1. The resulting secondstorage modulus transition (taken as the onset point of the lastdecrease in the storage modulus measured, i.e. second DMA modulustransition onset temperature) for the 50 KDa rCol polyurethane alloy was177.8° C., a 62.9° C. increase over the control sample described inExample 1.

Tensile testing was performed as outlined in Example 1. The averageYoung's modulus was 161 MPa, the average tensile stress measured was 17MPa, and the average elongation at break was 173% for the 50 KDa rColpolyurethane alloy.

EXAMPLE 43

A sample was prepared by dissolving 1 g of Native Trichoderma sp.Cellulase available from CREATIVE ENZYMES® (Cellulase-RG) into 5 mL ofde-ionized water and stirring with a magnetic stir bar at 1000 rpm for 1hour at 20° C. After stirring for 1 hour, 11.4 g of L3360 was added tothe solution and stirred at 1000 rpm for 30 minutes. The polyurethaneand cellulase solution was then pipetted into a Teflon evaporating dishwith a diameter of 10 cm. The dish was dried in an oven at 45° C.overnight. After drying, the dried sample was conditioned at standardreference atmosphere (23° C., 50% humidity) for 24 hours to create acellulase polyurethane alloy film.

DMA testing was performed as outlined in Example 1. The resulting secondstorage modulus transition (taken as the onset point of the lastdecrease in the storage modulus measured, i.e. second DMA modulustransition onset temperature) for the Celluase-RG polyurethane alloy was153.1° C., a 38.2° C. increase over the control sample described inExample 1.

Tensile testing was performed as outlined in Example 1. The averageYoung's modulus was 184 MPa, the average tensile stress measured was14.7 MPa, and the average elongation at break was 252% for the cellulasepolyurethane alloy.

EXAMPLE 44

A sample was prepared by dissolving 1 g of laboratory grade cellulaseavailable from Carolina Biological Supply Company (Cellulase-IG) into 5mL of de-ionized water and stirring with a magnetic stir bar at 1000 rpmfor 1 hour at 20° C. After stirring for 1 hour, 11.4 g of L3360 wasadded to the solution and stirred at 1000 rpm for 30 minutes. Thepolyurethane and cellulase solution was then pipetted into a Teflonevaporating dish with a diameter of 10 cm. The dish was dried in an ovenat 45° C. overnight. After drying, the dried sample was conditioned atstandard reference atmosphere (23° C., 50% humidity) for 24 hours tocreate a cellulase polyurethane alloy film.

DMA testing was performed as outlined in Example 1. The resulting secondstorage modulus transition (taken as the onset point of the lastdecrease in the storage modulus measured, i.e. second DMA modulustransition onset temperature) for the Cellulase-IG polyurethane alloywas 122.1° C., a 7.2° C. increase over the control sample described inExample 1.

Tensile testing was performed as outlined in Example 1. The averageYoung's modulus was 84 MPa, the average tensile stress measured was 15.1MPa, and the average elongation at break was 286% for the cellulasepolyurethane alloy.

EXAMPLE 45

Two control samples (Example No. 45a and Example No. 45b) were eachprepared according to the following process. 0.4 g of AF-715 (anantifoaming agent available from Quaker Color) was mixed into 38 g ofwaterborne polyurethane dispersion Hauthane HD-2001 from C.L. Hauthaway& Sons Corporation. The mixture was mixed using an impeller at a rate of500 rpm and allowed to stir for 5 minutes at room temperature. After themixture was properly mixed, 0.6 g BORCHI® Gel L 75 N was added toincrease the viscosity of the mixture and the mixture was allowed to mixfor 5 minutes. The mixture was then coated using a Mathis LTE-SLabcoater coater onto a release paper and was dried at 75° C. for 10minutes and at 100° C. for 10 minutes. The coating was then removed fromthe release paper to create a polyurethane film containing no protein.

After drying, the sample for Example 45a had a thickness of 0.4 mm andthe sample for Example 45b had a thickness of 0.4 mm. As reported inTable 7, the polyurethane film of Example 45a had a moisture vaportransmission rate of 30 g/m²/24 hr and polyurethane film of Example 45bhad a moisture vapor transmission rate of 38 g/m²/24 hr.

EXAMPLE 46

Two samples (Example No. 46a and Example No. 46b) were each preparedaccording to the following process. 13.25 g of gelatin from porcine skinwas dissolved in a solution of 2 g of antimicrobial Ultra-Fresh DW-56,0.8 g of AF-715 (an antifoaming agent available from Quaker Color), and75 mL of water at 50° C. The solution was stirred using an impeller at500 rpm until the gelatin was fully dissolved. The pH of the solutionwas then increased using 1M NaOH until a pH of 8-9 was achieved. Afteradjusting the pH, 77 g of waterborne polyurethane dispersion HauthaneHD-2001 from C.L. Hauthaway & Sons Corporation was added to the gelatinsolution and stirred for 15 minutes. After the gelatin and polyurethanesolution was properly mixed, 1 g of RM-4410 from Stahl was added toincrease the viscosity of the solution and the solution was mixed for 5minutes. The solution was then coated on a 0.35 mm thick microsuedetextile having a surface coated with a thin IMPRANIL® DLS coating layer(thickness of 0.03 mm). The gelatin polyurethane solution was coated ontop of the thin IMPRANIL® DLS coating layer using a handheld draw downapparatus and was allowed to dry at standard reference atmosphere (23°C. and 50% humidity) to create a gelatin-polyurethane film with atextile backing. The thin IMPRANIL® DLS coating was used to prevent thegelatin polyurethane coating from deeply penetrating into the microsuedetextile.

After drying, the sample for Example No. 46a had a thickness of 0.77 mm(which was the sum of the thicknesses for the gelatin-polyurethane film,the thin IMPRANIL® DLS coating, and the microsuede textile) and thesample for Example 46b had a thickness of 0.82 mm (which was the sum ofthe thicknesses for the gelatin-polyurethane film, the thin Impranil®DLS coating, and the microsuede textile).

As reported in Table 7, the sample for Example No. 46a had a moisturevapor transmission rate of 180 g/m²/24 hr, which was a 150 g/m²/24 hrincrease compared to the sample of Example No. 45a and a 142 g/m²/24 hrincrease compared to the sample of Example No. 45b. As also reported inTable 7, the sample for Example No. 46b had a moisture vaportransmission rate of 138 g/m²/24 hr, which was a 108 g/m²/24 hr increasecompared to the sample of Example No. 45a and a 100 g/m²/24 hr increasecompared to the sample of Example No. 45b.

Neither the thin IMPRANIL® DLS coating nor the microsuede textile had asignificant influence on the moisture vapor transmission rates for thesamples of Example Nos. 46a or 46b. In other words, the moisture vaportransmission rates reported in Table 7 reflect the moisture vaportransmission rates for only the gelatin-polyurethane films.

EXAMPLE 47

Two control samples (Example No. 47a and Example No. 47b) were eachprepared according to the following process. 0.4 g of AF-715 (anantifoaming agent available from Quaker Color) was mixed into 38 g ofwaterborne polyurethane dispersion L3360 from Hauthaway. The mixture wasmixed using an impeller at a rate of 500 rpm and allowed to stir for 5minutes at room temperature. After the mixture was properly mixed, 0.6 gBORCHI® Gel L 75 N was added to increase the viscosity of the mixtureand the mixture was allowed to mix for 5 minutes. The mixture was thencoated using a Mathis LTE-S Labcoater coater onto a release paper andwas dried at 75° C. for 10 minutes and at 100° C. for 10 minutes. Thecoating was then removed from the release paper to create a polyurethanefilm containing no protein.

After drying, the sample for Example No. 47a had a thickness of 0.32 mmand the sample for Example No. 47b had a thickness of 0.36 mm. Asreported in Table 7, the polyurethane film of Example No. 47a had amoisture vapor transmission rate of 23 g/m²/24 hr and polyurethane filmof Example No. 47b had a moisture vapor transmission rate of 27 g/m²/24hr.

EXAMPLE 48

Two samples (Example No. 48a and Example No. 48b) were each preparedaccording to the following process. 13.25 g of gelatin from porcine skinwas dissolved in a solution of 2 g of antimicrobial Ultra-Fresh DW-56,0.8 g of AF-715 (an antifoaming agent available from Quaker Color), and75 mL of water at 50° C. The solution was stirred using an impeller at500 rpm until the gelatin was fully dissolved. The pH of the solutionwas then increased using 1M NaOH until a pH of 8-9 was achieved. Afteradjusting the pH, 77 g of waterborne polyurethane dispersion L3360 fromHauthaway was added to the gelatin solution and stirred for 15 minutes.After the gelatin and polyurethane solution was properly mixed, 1 g ofRM-4410 from Stahl was added to increase the viscosity of the solutionand the solution was mixed for 5 minutes. The solution was then coatedon a 0.35 mm thick microsuede textile having a surface coated with athin IMPRANIL® DLS coating layer (thickness of 0.03 mm). The gelatin andpolyurethane solution was coated on top of the thin IMPRANIL® DLScoating layer using a handheld draw down apparatus and was allowed todry at standard reference atmosphere (23° C. and 50% humidity) to createa gelatin-polyurethane film with a textile backing. The thin IMPRANIL®DLS coating was used to prevent the gelatin polyurethane coating fromdeeply penetrating into the microsuede textile.

After drying, the sample for Example No. 48a had a thickness of 0.77 mm(which was the sum of the thicknesses for the gelatin-polyurethane film,the thin IMPRANIL® DLS coating, and the microsuede textile) and thesample for Example No. 48b had a thickness of 0.84 mm (which was the sumof the thicknesses for the gelatin-polyurethane film, the thin Impranil®DLS coating, and the microsuede textile).

As reported in Table 7, the sample for Example No. 48a had a moisturevapor transmission rate of 117 g/m²/24 hr, which was a 94 g/m²/24 hrincrease compared to the sample of Example No. 47a and a 90 g/m²/24 hrincrease compared to the sample of Example No. 47b. As also reported inTable 7, the sample for Example 48b had a moisture vapor transmissionrate of 74 g/m²/24 hr, which was a 51 g/m²/24 hr increase compared tothe sample of Example No. 47a and a 47 g/m²/24 hr increase compared tothe sample of Example No. 47b.

Neither the thin IMPRANIL® DLS coating nor the microsuede textile had asignificant influence on the moisture vapor transmission rates for thesamples of Example Nos. 46a or 46b. In other words, the moisture vaportransmission rates reported in Table 7 reflect the moisture vaportransmission rates for only the gelatin-polyurethane films.

EXAMPLE 49

Two control samples (Example No. 49a and Example No. 49b) were eachprepared according to the following process. 0.2 g of AF-715 (anantifoaming agent available from Quaker Color) was mixed into 38 g ofwaterborne polyurethane dispersion L3360 from Hauthaway. The mixture wasmixed using an impeller at a rate of 500 rpm for 5 minutes. After themixture was properly mixed, 0.6 g BORCHI® Gel L 75 N was added toincrease the viscosity of the mixture and the mixture was mixed againfor 5 minutes. This polyurethane mixture was then coated onto a releasepaper using a Mathis LTE-S Labcoater and allowed to dry at 75° C. for 10minutes and at 100° C. for 10 minutes.

Then a foam solution was then prepared by mixing waterborne polyurethanedispersion L3360 from Hauthaway with HeiQ Chemtex 2216-T (3% based onsolution weight), HeiQ Chemtex 2317 (3% based on solution weight), HeiQChemtex 2241-A (1% based on solution weight), and HeiQ Chemtex 2243(0.1% based on solution weight). This mixture was stirred for 5 minutesat room temperature using an impeller at 500 rpm. The mixture was thenfrothed to create a foamed mixture having a wet density between 700 g/Land 900 g/L. The foamed mixture was coated on the previously coatedpolyurethane layer using the Mathis LTE-S Labcoater and allowed to dryat 75° C. for 10 minutes and at 100° C. for 10 minutes. After this firstfoamed coating was dried, a second foamed coating layer made of the samefoamed mixture was coated on the first foamed coating using identicalconditions. After drying of the second foamed layer, the three-layersample was removed from the release paper.

The three-layer sample for Example No. 49a had a thickness of 0.23 mmand the three-layer sample for Example No. 49b had a thickness of 0.24mm. As reported in Table 7, the three-layer sample of Example No. 49ahad a moisture vapor transmission rate of 83 g/m²/24 hr and thethree-layer sample of Example No. 49b had a moisture vapor transmissionrate of 87 g/m²/24 hr.

EXAMPLE 50

Two samples (Example No. 50a and Example No. 50b) were each preparedaccording to the following process. 5.3 g of SUPRO® XT 221D soy proteinisolate was mixed with 30 g of water. The pH of the mixture was thenincreased using 1M NaOH until a pH of 8-9 was achieved. After adjustingthe pH, Ultra-Fresh DW-56 (15 wt % based on the soy protein isolatemass) and AF-715 antifoaming agent (1 wt % based on solution weight)were added and to the mixture, and the mixture was stirred using animpeller at 500 rpm until the soy protein isolate was fully dissolved.Once the soy protein isolate was fully dissolved, 32 g of waterbornepolyurethane dispersion L3360 from Hauthaway was added to the proteinsolution and the solution was stirred using an impeller at a rate of 500rpm for 10 minutes at room temperature. The protein solution was thencoated onto a release paper using a Mathis LTE-S Labcoater and allowedto dry at 75° C. for 10 minutes and at 100° C. for 10 minutes.

Then a foam solution was prepared by mixing 5.3 g SUPRO® XT 221D soyprotein isolate with 30 g of water. The pH of the mixture was increasedusing 1M NaOH until a pH of 8-9 was achieved. After adjusting the pH andonce the soy protein isolate was fully dissolved, Ultra-Fresh DW-56 (15wt % based on the soy protein mass), HeiQ Chemtex 2216-T (3 wt % basedon solution weight), HeiQ Chemtex 2317 (3% based on solution weight),HeiQ Chemtex 2241-A (1% based on solution weight), HeiQ Chemtex 2243(0.1% based on solution weight), 32 g of waterborne polyurethanedispersion L3360 from Hauthaway were added to the solution, and thesolution was stirred for 5 minutes at room temperature using an impellerat 500 rpm. This solution was then frothed to create a foam solutionwith a wet density between 700 g/L and 900 g/L. The foam solution wascoated on the previously coated protein solution layer using the MathisLTE-S Labcoater and allowed to dry at 75° C. for 10 minutes and at 100°C. for 10 minutes. After this first foamed solution coating was dried, asecond foam layer was coated on the first foamed coating using identicalconditions After drying of the second foam solution layer, thethree-layer sample was removed from the release paper.

The three-layer sample for Example No. 50a had a thickness of 0.24 mmand the three-layer sample for Example No. 50b had a thickness of 0.25mm. As reported in Table 7, the sample for Example No. 50a had amoisture vapor transmission rate of 268 g/m²/24 hr, which was a 185g/m²/24 hr increase compared to the sample of Example No. 49a and a 181g/m²/24 hr increase compared to the sample of Example No. 49b. As alsoreported in Table 7, the sample for Example No. 50b had a moisture vaportransmission rate of 277 g/m²/24 hr, which was a 194 g/m²/24 hr increasecompared to the sample of Example No. 49a and a 190 g/m²/24 hr increasecompared to the sample of Example No. 49b.

EXAMPLE 51

A control sample was prepared by mixing 0.4 g of AF-715 (an antifoamingagent available from Quaker Color) into 38 g of waterborne polyurethanedispersion IMPRAPERM® DL 5249 from Covestro. The mixture was mixed usingan impeller at a rate of 500 rpm and allowed to stir for 5 minutes atroom temperature. After the mixture was properly mixed, 0.6 g BORCHI®Gel L 75 N was added to increase the viscosity of the mixture and themixture was allowed to mix for 5 minutes. The mixture was then coatedusing a Mathis LTE-S Labcoater coater onto a release paper and was driedat 75° C. for 10 minutes and at 100° C. for 10 minutes. The coating wasthen removed from the release paper to create a polyurethane filmcontaining no protein.

After drying, the sample had a thickness of 0.08 mm. As reported inTable 7, the polyurethane film had a moisture vapor transmission rate of338 g/m²/24 hr.

EXAMPLE 52

Two samples (Example No. 52a and Example No. 52b) were each preparedaccording to the following process. 5.3 g of SUPRO® XT 221D soy proteinisolate was mixed with 30 g of water. The pH of the mixture was thenincreased using 1M NaOH until a pH of 8-9 was achieved. After adjustingthe pH, Ultra-Fresh DW-56 (15 wt % based on the soy protein isolatemass) and AF-715 antifoaming agent (1 wt % based on solution weight)were added and to the mixture, and the mixture was stirred using animpeller at 500 rpm until the soy protein isolate was fully dissolved.Once the soy protein isolate was fully dissolved, 32 g of waterbornepolyurethane dispersion IMPRAPERM® DL 5249 from Covestro was added tothe protein solution and the solution was stirred using an impeller at arate of 500 rpm for 10 minutes at room temperature. The protein solutionwas then coated onto a release paper using a Mathis LTE-S Labcoater andallowed to dry at 75° C. for 10 minutes and at 100° C. for 10 minutes.

Then a foam solution was prepared by mixing 5.3 g SUPRO® XT 221D soyprotein isolate with 30 g of water. The pH of the mixture was increasedusing 1M NaOH until a pH of 8-9 was achieved. After adjusting the pH andonce the soy protein isolate was fully dissolved, Ultra-Fresh DW-56 (15wt % based on the soy protein mass), HeiQ Chemtex 2216-T (3 wt % basedon solution weight), HeiQ Chemtex 2317 (3% based on solution weight),HeiQ Chemtex 2241-A (1% based on solution weight), HeiQ Chemtex 2243(0.1% based on solution weight), 32 g of waterborne polyurethanedispersion IMPRAPERM® DL 5249 from Covestro were added to the solution,and the solution was stirred for 5 minutes at room temperature using animpeller at 500 rpm. This solution was then frothed to create a foamedsolution with a wet density between 700 g/L and 900 g/L. The foamedsolution was coated on the previously coated protein solution layerusing the Mathis LTE-S Labcoater and allowed to dry at 75° C. for 10minutes and at 100° C. for 10 minutes. After this first foamed coatingwas dried, a second foamed layer was coated on the first foamed coatingusing identical conditions After drying of the second foamed solutionlayer, the three-layer sample was removed from the release paper.

The three-layer sample for Example No. 52a had a thickness of 0.22 mmand the three-layer sample for Example No. 52b had a thickness of 0.23mm. As reported in Table 7, the sample for Example 52a had a moisturevapor transmission rate of 626 g/m²/24 hr and the sample for Example 52bhad a moisture vapor transmission rate of 644 g/m²/24 hr. For purposesof evaluating a change in moisture vapor transmission rate, thesemoisture vapor transmission rates for Example Nos. 52a and 52b can becompared to the moisture vapor transmission rate of Example No. 51because all three samples included a non-foamed layer made usingIMPRAPERM® DL 5249 and having substantially the same thickness. Thefoamed layers of Example Nos. 52a and 52b did not have a significantinfluence on the moisture vapor transmission rates for these samplesbecause of their high degree of porosity. Compared to the sample ofExample No. 51, the sample of Example No. 52a showed a 288 g/m²/24 hrincrease in moisture vapor transmission and the sample of Example No.52b showed a 306 g/m²/24 hr increase in moisture vapor transmission.

EXAMPLE 53

A control sample was prepared by mixing 0.2 g of AF-715 (an antifoamingagent available from Quaker Color) into 38 g of waterborne polyurethanedispersion IMPRAPERM® DL 5249 from Covestro. The mixture was mixed usingan impeller at a rate of 500 rpm for 5 minutes. After the mixture wasproperly mixed, 0.6 g BORCHI® Gel L 75 N was added to increase theviscosity of the mixture and the mixture was mixed again for 5 minutes.This polyurethane mixture was then coated onto a release paper using aMathis LTE-S Labcoater and allowed to dry at 75° C. for 10 minutes andat 100° C. for 10 minutes.

Then a foam solution was then prepared by mixing waterborne polyurethanedispersion L3360 from Hauthaway with HeiQ Chemtex 2216-T (3% based onsolution weight), HeiQ Chemtex 2317 (3% based on solution weight), HeiQChemtex 2241-A (1% based on solution weight), and HeiQ Chemtex 2243(0.1% based on solution weight). This mixture was stirred for 5 minutesat room temperature using an impeller at 500 rpm. The mixture was thenfrothed to create a foamed mixture having a wet density between 700 g/Land 900 g/L. The foamed mixture was coated on the previously coatedpolyurethane layer using the Mathis LTE-S Labcoater and allowed to dryat 75° C. for 10 minutes and at 100° C. for 10 minutes. After this firstfoamed coating was dried, a second foamed coating layer made of the sameL3360 foamed mixture was coated on the first foamed coating usingidentical conditions. After drying of the second foamed layer, thethree-layer sample was removed from the release paper.

The three-layer sample for Example No. 53 had a thickness of 0.32 mm. Asreported in Table 7, the three-layer sample of Example No. 53 had amoisture vapor transmission rate of 84 g/m²/24 hr.

EXAMPLE 54

A sample was prepared by mixing 5.3 g of SUPRO® XT 221D soy proteinisolate with 30 g of water. The pH of the mixture was increased using 1MNaOH until a pH of 8-9 was achieved. After adjusting the pH, Ultra-FreshDW-56 (15 wt % based on the soy protein isolate mass) and AF-715antifoaming agent (1 wt % based on solution weight) were added and tothe mixture, and the mixture was stirred using an impeller at 500 rpmuntil the soy protein isolate was fully dissolved. Once the soy proteinisolate was fully dissolved, 53.7 g of waterborne polyurethanedispersion IMPRAPERM® DL 5249 from Covestro was added to the proteinsolution and the solution was stirred using an impeller at a rate of 500rpm for 10 minutes at room temperature. The protein solution was thencoated onto a release paper using a Mathis LTE-S Labcoater and allowedto dry at 75° C. for 10 minutes and at 100° C. for 10 minutes.

Then a foam solution was prepared by mixing 5.3 g SUPRO® XT 221D soyprotein isolate with 30 g of water. The pH of the mixture was increasedusing 1M NaOH until a pH of 8-9 was achieved. After adjusting the pH andonce the soy protein isolate was fully dissolved, Ultra-Fresh DW-56 (15wt % based on the soy protein mass), HeiQ Chemtex 2216-T (3 wt % basedon solution weight), HeiQ Chemtex 2317 (3% based on solution weight),HeiQ Chemtex 2241-A (1% based on solution weight), HeiQ Chemtex 2243(0.1% based on solution weight), 53.7 g of waterborne polyurethanedispersion L3360 from Hauthaway were added to the solution, and thesolution was stirred for 5 minutes at room temperature using an impellerat 500 rpm. This solution was then frothed to create a foamed solutionwith a wet density between 700 g/L and 900 g/L. The foamed solution wascoated on the previously coated protein solution layer using the MathisLTE-S Labcoater and allowed to dry at 75° C. for 10 minutes and at 100°C. for 10 minutes. After this first foamed solution coating was dried, asecond foam L3360 layer was coated on the first foamed coating usingidentical conditions After drying of the second foam solution layer, thethree-layer sample was removed from the release paper.

The three-layer sample for Example No. 54 had a thickness of 0.32 mm. Asreported in Table 7, the sample for Example No. 54 had a moisture vaportransmission rate of 166 g/m²/24 hr, which was a 82 g/m²/24 hr increasecompared to the sample of Example No. 53. The graph of FIG. 23 showsthat the breathability for the sample of Example No. 54 is consistentover time. The amount of water transported through the sample increasedlinearly with time during the breathability test. The graph of FIG. 23shows that the protein in the protein polyurethane alloy does not causeany significant fluctuations in the alloy's breathability over time.

EXAMPLE 55

A control sample was prepared by mixing 0.4 g of AF-715 (an antifoamingagent from Quaker Color) into 38 g of waterborne polyurethane dispersioncomposed of 25 wt % IMPRAPERM® DL 5249 from Covestro and 75 wt % L3360from Hauthaway. The mixture was mixed using an impeller at a rate of 500rpm and allowed to stir for 5 minutes at room temperature. After themixture was properly mixed, 0.6 g BORCHI® Gel L 75 N was added toincrease the viscosity of the mixture and the mixture was allowed to mixfor 5 minutes. The mixture was then coated using a Mathis LTE-SLabcoater coater onto a release paper and was dried at 75° C. for 10minutes and at 100° C. for 10 minutes. The coating was then removed fromthe release paper to create a polyurethane film containing no protein.

After drying, the sample had a thickness of 0.07 mm. As reported inTable 7, the polyurethane film had a moisture vapor transmission rate of168 g/m²/24 hr.

EXAMPLE 56

A sample was prepared by mixing 5.3 g of SUPRO® XT 221D soy proteinisolate with 30 g of water. The pH of the mixture was increased using 1MNaOH until a pH of 8-9 was achieved. After adjusting the pH, Ultra-FreshDW-56 (15 wt % based on the soy protein isolate mass) and AF-715antifoaming agent (1 wt % based on solution weight) were added and tothe mixture, and the mixture was stirred using an impeller at 500 rpmuntil the soy protein isolate was fully dissolved. Once the soy proteinisolate was fully dissolved, 53.7 g of waterborne polyurethanedispersion composed of 25 wt % IMPRAPERM® DL 5249 from Covestro and 75wt % L3360 from Hauthaway was added to the protein solution and thesolution was stirred using an impeller at a rate of 500 rpm for 10minutes at room temperature. The protein solution was then coated onto arelease paper using a Mathis LTE-S Labcoater and allowed to dry at 75°C. for 10 minutes and at 100° C. for 10 minutes.

After drying, the sample had a thickness of 0.05 mm. As reported inTable 7, the sample had a moisture vapor transmission rate of 266g/m²/24 hr, which was a 98 g/m²/24 hr increase compared to the sample ofExample No. 55.

EXAMPLE TABLES

The following Tables 3-6 report the DMA and mechanical property testresults for Example Nos. 1-31. The “Sancure” polyurethane in the tablesis SANCURE™ 20025F, an aliphatic polyester polyurethane dispersion at47% solids in water from Lubrizol. The “Impranil DLS” polyurethane isIMPRANIL® DLS, an aliphatic polyester polyurethane with 50% solidscontent in water from Covestro. The “L2996” polyurethane is an aliphaticpolycarbonate polyurethane dispersion with 35% solids content in waterfrom Hauthaway. The “Gelatin” protein is type A porcine skin gelatinG2500 from Sigma. The “SPI” protein is soy protein isolate IC90545625from MP Medicals. The “Collagen” protein is bovine collagen from WuxiBIOT biology technology in China. The “BSA” protein is bovine serumalbumin 5470 from Sigma. The “rCol” protein recombinant bovine collagenprepared in yeast from Modern Meadow. The “Albumin” protein is chickenegg white albumin A5253 from Sigma. The “Pea” protein is pea proteinpowder MTX5232 from Bobs Red Mills. The “Peanut” protein is peanutprotein powder from Tru-Nut. Table 7 reports the moisture vaportransmission rate test results for Example Nos. 45-56.

TABLE 3 Second DMA Modulus Transition Onset Temperatures 2nd ModulusDelta 2nd Transition Modulus Protein PU Onset Transition Ex. No. PUProtein (wt %) (wt %) (° C.) Onset 1 L3360 None  0% 100%  114.9 — 2UD-108 None  0% 100%  127.4 — 3 UD-250 None  0% 100%  160.8 — 4 UD-303None  0% 100%  158.1 — 5 Impranil DLS None  0% 100%  146.4 — 6 SancureNone  0% 100%  49.6 — 7 HD-2001 None  0% 100%  128 — 8 L2996 None  0%100%  186.2 — 9 L3360 Gelatin 30% 70% 180.6 65.7 10 UD-108 Gelatin 30%70% 184.9 57.5 11 UD-250 Gelatin 30% 70% 186.1 25.3 12 Impranil DLSGelatin 30% 70% 190.4 44 13 UD-303 Gelatin 30% 70% 179.5 21.4 14 SancureGelatin 30% 70% 188 138.4 15 HD2001 Gelatin 30% 70% 184.9 56.9 16 L2996Gelatin 30% 70% 187.1 — 17 L3360 Collagen 30% 70% 180.3 65.4 18 L3360rCol 30% 70% 175.4 60.5 19 L3360 Albumen 30% 70% 168.4 53.5 20 L3360 BSA30% 70% 184.9 70 21 L3360 SPI (pH 10) 30% 70% 186.6 71.7 22 L3360 Pea30% 70% 186.2 71.3 23 L3360 Peanut 30% 70% 151.92 37 24 L3360 Gelatin50% 50% — — 35 L3360 Gelatin 20% 80% 184 69.1 26 L3360 Gelatin 15% 85%138.3 23.4 27 L3360 Gelatin 10% 90% 122.9 8 28 L3360 Gelatin  5% 95%134.2 19.3 29 L3360 Gelatin  1% 99% — — 30 L3360 SPI raw 10% 90% 133.919 31 L3360 SPI (pH 8) 20% 80% 187.1 72.2 42 L3360 50 KDa rCol 30% 70%177.8 62.9 43 L3360 Cellulase-RG 20% 80% 153.1 38.2 44 L3360Cellulase-IG 20% 80% 122.1 7.2

TABLE 4 First DMA Modulus Transition Onset Temperatures & Soft Phasetan(δ) Peak Temperatures 1st Delta Delta 1st Tan(δ) Modulus Tan(δ)Modulus peak Transition Peak Transition Protein PU Temp. Onset Temp.Onset Ex. No. PU Protein (wt %) (wt %) (° C.) (° C.) (° C.) (° C.) 1L3360 None  0% 100%  −33 −50 — — 2 UD-108 None  0% 100%  −46 −58 — — 3UD-250 None  0% 100%  −30 — — — 4 UD-303 None  0% 100%  −45 −59 — — 5Impranil DLS None  0% 100%  −29 −44 — — 6 Sancure None  0% 100%  −39 −50— — 7 HD-2001 None  0% 100%  −20 −35 — — 8 L2996 None  0% 100%  −20 — —— 9 L3360 Gelatin 30% 70% −39 −53 −6 −3 10 UD-108 Gelatin 30% 70% −47−57 −1 1 11 UD-250 Gelatin 30% 70% −30 — 0 — 12 Impranil DLS Gelatin 30%70% −36 −47 −7 −3 13 UD-303 Gelatin 30% 70% −52 −63 −7 −4 14 SancureGelatin 30% 70% −46 −55 −7 −5 15 HD2001 Gelatin 30% 70% −20 −36 0 −1 16L2996 Gelatin 30% 70% 17 L3360 Collagen 30% 70% −35 −49 −2 1 18 L3360rCol 30% 70% −33 −49 0 1 19 L3360 Albumen 30% 70% −36 −52 −3 −2 20 L3360BSA 30% 70% −35 −49 −2 1 21 L3360 SPI (pH 10) 30% 70% −38 −53 −5 −3 22L3360 Pea 30% 70% −33 −52 0 −2 23 L3360 Peanut 30% 70% −41 −53 −8 −3 24L3360 Gelatin 50% 50% −38 −52 −5 −2 25 L3360 Gelatin 20% 80% −32 −49 1 126 L3360 Gelatin 15% 85% −34 −51 −1 −1 27 L3360 Gelatin 10% 90% −33 −470 3 28 L3360 Gelatin  5% 95% −34 −49 −1 1 29 L3360 Gelatin  1% 99% — — —— 30 L3360 SPI raw 10% 90% −36 −49 −3 1 31 L3360 SPI (pH 8) 20% 80% −36−51 −3 −1 42 L3360 50 KDa rCol 30% 70% −31 −47 2 3 43 L3360 Cellulase-RG20% 80% −34 −48 −1 2 44 L3360 Cellulase-IG 20% 80% −33 −48 0 2

TABLE 5 Tensile Strength Tensile Delta % Delta Protein PU StrengthTensile Tensile Ex. No. PU Protein (wt %) (wt %) (MPa) Strength Strength1 L3360 None  0% 100%  12.9 — — 2 UD-108 None  0% 100%  19.4 — — 3UD-250 None  0% 100%  26.4 — — 4 UD-303 None  0% 100%  16.7 — — 5Impranil DLS None  0% 100%  15.1 — — 6 Sancure None  0% 100%  1.4 — — 7HD-2001 None  0% 100%  33 — — 8 L2996 None  0% 100%  — — — 9 L3360Gelatin 30% 70% 19.8 6.9 53.8 10 UD-108 Gelatin 30% 70% 23.1 3.7 19.1 11UD-250 Gelatin 30% 70% — — — 12 Impranil DLS Gelatin 30% 70% 17.9 2.818.5 13 UD-303 Gelatin 30% 70% 23.2 6.5 38.9 14 Sancure Gelatin 30% 70%15.3 13.9 993 15 HD2001 Gelatin 30% 70% 17.9 −15.1 −45.8 16 L2996Gelatin 30% 70% — — — 17 L3360 Collagen 30% 70% 17.3 4.4 34.4 18 L3360rCol 30% 70% 16.8 3.9 29.9 19 L3360 Albumen 30% 70% 14.8 1.9 14.9 20L3360 BSA 30% 70% 11.7 −1.2 −9.1 21 L3360 SPI (pH 10) 30% 70% 18.2 5.341.1 22 L3360 Pea 30% 70% 15.3 2.4 18.4 23 L3360 Peanut 30% 70% 11 −1.9−14.5 24 L3360 Gelatin 50% 50% — — — 25 L3360 Gelatin 20% 80% 17.2 4.333.5 26 L3360 Gelatin 15% 85% 16 3.1 24.3 27 L3360 Gelatin 10% 90% 16.83.9 29.9 28 L3360 Gelatin  5% 95% 11.2 −1.7 −13 29 L3360 Gelatin  1% 99%11.8 −1.1 −8.7 30 L3360 SPI raw 10% 90% 14.6 1.7 13.4 31 L3360 SPI (pH8) 20% 80% 18 5.1 39.3 42 L3360 50 KDa rCol 30% 70% 17 4.1 31.8 43 L3360Cellulase-RG 20% 80% 14.7 1.8 14 44 L3360 Cellulase-IG 20% 80% 15.1 2.217

TABLE 6 Young's Modulus Young's Delta % Delta Protein PU Modulus Young'sYoung's Ex. No. PU Protein (wt %) (wt %) (MPa) Modulus Modulus 1 L3360None  0% 100%  59 — — 2 UD-108 None  0% 100%  23 — — 3 UD-250 None  0%100%  557 — — 4 UD-303 None  0% 100%  27 — — 5 Impranil DLS None  0%100%  13 — — 6 Sancure None  0% 100%  337 — — 7 HD-2001 None  0% 100% 20 — — 8 L2996 None  0% 100%  − — — 9 L3360 Gelatin 30% 70% 344 285 47810 UD-108 Gelatin 30% 70% 324 301 1308 11 UD-250 Gelatin 30% 70% — — —12 Impranil DLS Gelatin 30% 70% 326 313 2407 13 UD-303 Gelatin 30% 70%379 352 1304 14 Sancure Gelatin 30% 70% 579 242 71.8 15 HD2001 Gelatin30% 70% 115 95 475 16 L2996 Gelatin 30% 70% — — — 17 L3360 Collagen 30%70% 226 167 280 18 L3360 rCol 30% 70% 169 110 184 19 L3360 Albumen 30%70% 204 145 243 20 L3360 BSA 30% 70% 174 114 192 21 L3360 SPI (pH 10)30% 70% 396 337 566 22 L3360 Pea 30% 70% 163 104 175 23 L3360 Peanut 30%70% 87 28 47 24 L3360 Gelatin 50% 50% — — — 25 L3360 Gelatin 20% 80% 12970 117 26 L3360 Gelatin 15% 85% 93 33 56 27 L3360 Gelatin 10% 90% 71 1119 28 L3360 Gelatin  5% 95% 51 −9 −14 29 L3360 Gelatin  1% 99% 54 −5 −930 L3360 SPI raw 10% 90% 95 36 60 31 L3360 SPI (pH 8) 20% 80% 223 164275 42 L3360 50 KDa rCol 30% 70% 161 102 173 43 L3360 Cellulase-RG 20%80% 184 125 212 44 L3360 Cellulase-IG 20% 80% 84 25 42

TABLE 7 Moisture Vapor Transmission Rate (MVTR) Protein PU MVTR Delta %Delta Ex. No. PU Protein (wt %) (wt %) (g/m²/24 hr) MVTR MVTR 45aHD-2001 None  0% 100%  30 — — 45b HD-2001 None  0% 100%  38 — — 46aHD-2001 Gelatin 30% 70% 180 142-150 374-500 46b HD-2001 Gelatin 30% 70%138 100-108 263-360 47a L3360 None  0% 100%  23 — — 47b L3360 None  0%100%  27 — — 48a L3360 SPI 30% 70% 117 90-94 333-409 48b L3360 SPI 30%70% 74 47-51 174-222 49a L3360 None  0% 100%  83 — — 49b L3360 None  0%100%  87 — — 50a L3360 SPI 30% 70% 268 181-185 208-223 50b L3360 SPI 30%70% 277 190-194 218-233 51  Impraperm None  0% 100%  338 — — 5249 52aImpraperm SPI 30% 70% 626 288  85 5249 52b Impraperm SPI 30% 70% 644306  91 5249 53  Impraperm None  0% 100%  84 — — 5249 & L- 3360 54 Impraperm SPI 20% 80% 166 82 98 5249 & L- 3360 55  Impraperm None  0%100%  168 — — 5249 & L- 3360 56  Impraperm SPI 20% 80% 266 98 58 5249 &L- 3360

While various embodiments have been described herein, they have beenpresented by way of example, and not limitation. It should be apparentthat adaptations and modifications are intended to be within the meaningand range of equivalents of the disclosed embodiments, based on theteaching and guidance presented herein. It therefore will be apparent toone skilled in the art that various changes in form and detail can bemade to the embodiments disclosed herein without departing from thespirit and scope of the present disclosure. The elements of theembodiments presented herein are not necessarily mutually exclusive, butcan be interchanged to meet various situations as would be appreciatedby one of skill in the art.

Embodiments of the present disclosure are described in detail hereinwith reference to embodiments thereof as illustrated in the accompanyingdrawings, in which like reference numerals are used to indicateidentical or functionally similar elements. References to “oneembodiment,” “an embodiment,” “some embodiments,” “in certainembodiments,” etc., indicate that the embodiment described can include aparticular feature, structure, or characteristic, but every embodimentcan not necessarily include the particular feature, structure, orcharacteristic. Moreover, such phrases are not necessarily referring tothe same embodiment. Further, when a particular feature, structure, orcharacteristic is described in connection with an embodiment, it issubmitted that it is within the knowledge of one skilled in the art toaffect such feature, structure, or characteristic in connection withother embodiments whether or not explicitly described.

The examples are illustrative, but not limiting, of the presentdisclosure. Other suitable modifications and adaptations of the varietyof conditions and parameters normally encountered in the field, andwhich would be apparent to those skilled in the art, are within thespirit and scope of the disclosure.

It is to be understood that the phraseology or terminology used hereinis for the purpose of description and not of limitation. The breadth andscope of the present disclosure should not be limited by any of theabove-described exemplary embodiments, but should be defined inaccordance with the following claims and their equivalents.

SEQUENCES Human Collagen alpha-1 (III) chain SEQ ID NO: 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

1-29. (canceled)
 30. A soy protein polyurethane alloy, comprising a soyprotein dissolved within a polyurethane, wherein the soy proteinpolyurethane alloy has a Dynamic Mechanical Analysis (DMA) tan(δ) peakat a temperature ranging from about −60° C. to about 30° C. and a secondDMA modulus transition onset temperature ranging from about 130° C. toabout 200° C.
 31. The soy protein polyurethane alloy of claim 30,wherein the soy protein polyurethane alloy is transparent.
 32. The soyprotein polyurethane alloy of claim 30, wherein the polyurethane has aYoung's modulus in the absence of soy protein, and wherein the soyprotein polyurethane alloy has a Young's modulus ranging from about 60%to about 570% greater than the Young's modulus of the polyurethane inthe absence of soy protein.
 33. The soy protein polyurethane alloy ofclaim 30, wherein the polyurethane has a Young's modulus in the absenceof soy protein, and wherein the soy protein polyurethane alloy has aYoung's modulus ranging from about 35 MPa to about 340 MPa greater thanthe Young's modulus of the polyurethane in the absence of soy protein.34. The soy protein polyurethane alloy of claim 30, wherein the soyprotein polyurethane alloy has a Young's modulus ranging from about 90MPa to about 400 MPa.
 35. The soy protein polyurethane alloy of claim30, wherein the polyurethane has a second DMA modulus transition onsettemperature in the absence of soy protein, and wherein the second DMAmodulus transition onset temperature of the soy protein polyurethanealloy ranges from about 15° C. to about 100° C. greater than the secondDMA modulus transition onset temperature of the polyurethane in theabsence of soy protein.
 36. The soy protein polyurethane alloy of claim30, wherein the polyurethane has a tensile strength in the absence ofsoy protein, and wherein the soy protein polyurethane alloy has atensile strength ranging from about 10% to about 45% greater than thetensile strength of the polyurethane in the absence of soy protein. 37.The soy protein polyurethane alloy of claim 30, wherein the polyurethanehas a tensile strength in the absence of soy protein, and wherein thesoy protein polyurethane alloy has a tensile strength ranging from about1.5 MPa to about 5.5 MPa greater than the tensile strength of thepolyurethane in the absence of soy protein.
 38. The soy proteinpolyurethane alloy of claim 30, wherein the soy protein polyurethanealloy has a tensile strength ranging from about 14 MPa to about 19 MPa.39. The soy protein polyurethane alloy of claim 30, comprising about 10wt % to about 50 wt % of the soy protein and about 50 wt % to about 90wt % of the polyurethane.
 40. The soy protein polyurethane alloy ofclaim 30, comprising about 20 wt % to about 35 wt % of the soy proteinand about 65 wt % to about 80 wt % of the polyurethane.
 41. The soyprotein polyurethane alloy of claim 30, wherein the polyurethane has amoisture vapor transmission rate in the absence of protein, and whereinthe soy protein polyurethane alloy has a moisture vapor transmissionrate ranging from about 20% to about 600% greater than the moisturevapor transmission rate of the polyurethane in the absence of protein.42. The soy protein polyurethane alloy of claim 30, wherein thepolyurethane has a moisture vapor transmission rate in the absence ofprotein, and wherein the soy protein polyurethane alloy has a moisturevapor transmission rate ranging from about 30 g/m²/24 hr to about 500g/m²/24 hr greater than the moisture vapor transmission rate of thepolyurethane in the absence of protein.
 43. The soy protein polyurethanealloy of claim 30, wherein the soy protein polyurethane alloy has amoisture vapor transmission rate ranging from about 30 g/m²/24 hr toabout 1000 g/m²/24 hr.
 44. The soy protein polyurethane alloy of claim30, wherein the soy protein is soy protein isolate.
 45. The soy proteinpolyurethane alloy of claim 30, wherein the soy protein is a chemicallymodified soy protein isolate.